CN101454727B - Toner - Google Patents

Abstract

An object of the present invention is to provide a toner which: is excellent in fixing ability such as low-temperature fixability, hot offset property, and separability even in a fixing system excellent in quick start property and energy saving property; has high gloss; and is excellent in development stability and transferability irrespective of environments. The toner of the present invention includes toner particles each containing at least a binder resin and a colorant, in which, in a case where a tetrahydrofuran (THF) insoluble matter of the binder resin in the toner when the toner is subjected to Soxhlet extraction with THF for 2 hours is represented by A (mass%), a THF insoluble matter of the binder resin in the toner when the toner is subjected to Soxhlet extraction with THF for 4hours is represented by B (mass%), a THF insoluble matter of the binder resin in the toner when the toner is subjected to Soxhlet extraction with THF for 8 hours is represented by C (mass%), and a THF insoluble matter of the binder resin in the toner when the toner is subjected to Soxhlet extraction with THF for 16 hours is represented by D (mass%), A, B, C, and D satisfy the following expression: (A - B)/2 > (B - C)/4 > (C - D)/8 where 40 < A 75 (mass%) and 1.0 < D < 40 (masts%).

Description

Toner

Technical field

The present invention relates to be used for the toner of image forming method, described image forming method comprises at least: make the latent electrostatic image developing that is formed on electrostatic latent image bearing carrier such as electrophotographic photosensitive element or the electrostatic recording inductor (electrostaticrecording derivative) with developer in electrophotographic method, to form the development step of toner image on the electrostatic latent image bearing carrier; By or will not be formed at the transfer step of toner image static printing to the recording materials on the electrostatic latent image bearing carrier by intermediate transfer member; With the photographic fixing step that under heating, makes the toner image on the recording materials.

Background technology

In recent years, for office's application target and individual application target, and as arbitrary market of drawing market and light printing market in the image forming apparatus of the employing electrophotographic method that extensively needs be excellent image forming system on startability and energy saving fast.

Therefore, from reducing the viewpoint of energy consumption, the main flow of particularly photographic fixing system changes light compression set shadow system such as film photographic fixing or the band photographic fixing (for example referring to JP2005-055523 A and JP2005-056596 A) with little thermal capacity into from the hard roller system that tradition has big thermal capacity.

Because this light compression set shadow system has little thermal capacity, so shortening system temperature, this system reaches the time (hereinafter can be referred to as " adjusting temperature ") that the photographic fixing design temperature needs, and quick startability excellence.In addition, described system has the following advantages: this can reduce fixation unit on size and weight, and this is because system does not resemble the hard roller system of tradition, does not use thick metal parts or a plurality of well heater.

Yet on the other hand, because thermal capacity reduces, light compression set shadow system is than the reduction that shows bigger fixing member surface temperature under the situation of the hard roller system of tradition when duplicating continuously.In addition, light compression set shadow system is tending towards reducing the pressure that will be applied to the toner on the recording materials, and therefore bad photographic fixing is easy to take place.

On the contrary, in the film photographic fixing outside the light compression set shadow system for example, proposed a kind of fixing member, the toner image on its abundant photographic fixing recording materials reduces (for example referring to JP2005-056738 A) with the temperature of the location (hereinafter can be called " fusing nip ") that prevents to contact with each other at fixing member and pressing element.Yet this light compression set shadow system is easy to also cause that the fixing member surface temperature reduces, the fixing temperature at the fusing nip place distribute compare with the hard roller system of photographic fixing pressure distribution and tradition be easy to inhomogeneous.Therefore, be easy to take place because temperature reduces, or the bad photographic fixing that causes of the stained phenomenon of so-called heat, the stained phenomenon of described heat is: toner adheres on the fixing member with the fusing nip portion that surpasses the temperature of regulating temperature to pollute fixing member, the fixing member of pollution pollution recording materials when fixing member contacts with recording materials again.Proposed various inventions and reduced, and this fixing temperature in fusing nip portion is distributed and photographic fixing pressure distribution homogenising to prevent aforesaid this temperature, but the additional improvement of the described invention of needs.

Therefore, the performance that the low-temperature fixing of additional improvement and wide fixing temperature scope (hereinafter can be called " photographic fixing the scope ") toner of respectively doing for oneself need always is so that toner not only is suitable for the hard roller system of tradition but also is suitable for the light compression set shadow system of energy saving excellence.

In addition, the additional improvement that in the image forming apparatus that adopts electrophotographic method, needs speed and picture quality in recent years.Yet, consider corresponding rapid development system, the improvement of development capability and aforesaid low-temperature fixing be improved to equilibrium relation.For example, under the toner situation that low-temperature fixing is put in the first place, the molecular weight distribution of resin glue is tending towards diminishing, or the softening point of resin is tending towards reducing.As a result, being easy to take place harmful effect such as toner deterioration and developing member when rapid development pollutes.On the contrary, under the toner situation that development capability is put in the first place, it is big that the molecular weight distribution of resin glue is tending towards becoming, or the softening point of resin glue is tending towards increasing.As a result, the low-temperature fixing deterioration of toner, so it becomes difficult to achieve the image forming system of energy saving excellence.

Consider aforementionedly, the toner that is suitable for rapid development system and light compression set shadow system requires highly compatible between photographic fixing ability and the development capability to meet market demand.

Various inventions have been proposed traditionally to be provided for realizing the toner of compatibility between photographic fixing ability and the development capability.For example, a large amount of toners that are used in combination low softening point resin and high softening point resin separately and utilize the character of each resin have separately been proposed.These toners are intended to realize the compatibility between photographic fixing ability and the development capability separately, and the improvement of the hot stained property of the improvement of the low-temperature fixing by low softening point resin and high softening point resin is simultaneously guaranteed the photographic fixing scope and kept balance between the described improvement.

In these are proposed, some proposals relate to the toner that is used in combination two or more resins separately and has so-called island structure separately, in described island structure, low softening point resin is included in the structure of high softening point resin (for example referring to JP2002-214833 A and JP2002-244338 A).Each leisure of these toners is controlled the stripping of low softening point resin and is guaranteed that photographic fixing scope aspect is excellent.Yet, need the additional improvement of low-temperature fixing so that each toner can be adapted to aforesaid this light compression set shadow system.

In addition, as follows about another proposal of the toner that is used in combination low softening point resin and high softening point resin: the good resin of compatibility is used in combination low-temperature fixing and the bin stability (for example referring to JP2000-275908 A and JP2004-085605 A) that satisfies toner between two or more.Yet aspect the improvement of guaranteeing photographic fixing scope in above-mentioned light compression set shadow system and the development capability in the rapid development system, it is not enough that this proposal remains.

Therefore, at present, still there is problem about highly compatible between photographic fixing ability and the development capability.

Summary of the invention

The problem to be solved in the present invention

The purpose of this invention is to provide toner, its: even even in the light compression set shadow system neutralization of fast startability and energy saving excellence in the rapid development system, the photographic fixing ability also is excellent as low-temperature fixing, hot stained property and separation property; Have high gloss and high chroma; And no matter how stable developing also is excellent to environment.

The means of dealing with problems

Described purpose can realize by following component of the present invention.

(1) a kind of toner, it comprises the toner-particle that comprises resin glue and colorant separately at least, wherein, when making described toner carry out soxhlet extraction (Soxhlet extraction) in the time of 2 hours with THF, the tetrahydrofuran of the resin glue in toner (THF) insoluble substance is represented by A (quality %), when making described toner carry out soxhlet extraction in the time of 4 hours with THF, the THF insoluble substance of the resin glue in toner is represented by B (quality %), when making described toner carry out soxhlet extraction in the time of 8 hours with THF, the THF insoluble substance of the resin glue in toner is represented by C (quality %), and when making described toner carry out soxhlet extraction in the time of 16 hours with THF, under the situation of THF insoluble substance in the resin glue in toner by D (quality %) expression, A, B, C and D satisfy following expression formula (1):

(A-B)/2>(B-C)/4>(C-D)/8 (1)

Wherein 40＜A≤75 (quality %) and 1.0＜D＜40 (quality %);

(2), locate to have the highest endothermic peak at 50 to 110 ℃ in the endothermic curve of wherein said toner in differential scanning calorimetry (DSC) according to the described toner of project (1).

(3) according to the described toner of project (1), storage elastic modulus G ' (140 ℃) of wherein said toner under 140 ℃ are 1.0 * 10 ³DN/m ²Below to being lower than 1.0 * 10 ⁵DN/m ²

(4) according to the described toner of project (1), wherein said toner has more than 0.945 to the average circularity below 0.990, described average circularity is by following acquisition: more than 0.200 to the circularity scope below 1.000, will be that the circularity that the streaming particle image measurement mechanism of 512 * 512 pixels (every pixel 0.37 μ m * 0.37 μ m) is measured is divided into 800 parts and analyzes described circularity with having Flame Image Process resolution; With

(5) according to the described toner of project (1), wherein said resin glue has low softening point resin and high softening point resin, described low softening point resin has more than 80.0 ℃ to being lower than 110.0 ℃ softening point and having polyester unit and the vinyl-based copolymer unit, and described high softening point resin has more than 110.0 ℃ to the softening point below 145.0 ℃ and has polyester unit and the vinyl-based copolymer unit.

Effect of the present invention

According to the present invention, can obtain a kind of image, its: even even in the light compression set shadow system neutralization of fast startability and energy saving excellence in the rapid development system, the photographic fixing ability also is excellent as low-temperature fixing, hot stained property and separation property; And have high gloss and a high chroma.In addition, regardless of environment, the stable developing excellence of described image.In addition, according to the present invention, additional improvement prevents for example generation of fixing member pollution, and can obtain good image for a long time from the separation property of fixing member.

Description of drawings

In the accompanying drawings:

Fig. 1 be illustrate expression toner of the present invention improved the photographic fixing ability effect at explanatory view with the stripping curve in the THF soxhlet extraction;

Fig. 2 illustrates the explanatory view that toner of the present invention is carried out the fixation unit example of photographic fixing merit rating;

Fig. 3 illustrates the explanatory view that toner of the present invention is carried out the image example of photographic fixing merit rating;

Fig. 4 illustrates the explanatory view that toner of the present invention is carried out the image example of photographic fixing merit rating;

Fig. 5 illustrates the explanatory view that toner of the present invention is carried out the image example of photographic fixing merit rating;

Fig. 6 illustrates the explanatory view that toner of the present invention is carried out the image example of photographic fixing ability and transfer printing merit rating;

Fig. 7 illustrates the explanatory view that toner of the present invention is carried out the image example of transfer printing merit rating;

Fig. 8 is the explanatory view that the image forming apparatus example that uses toner of the present invention is shown;

Fig. 9 is the explanatory view that the image forming apparatus example that uses toner of the present invention is shown;

Figure 10 is the explanatory view that the image forming apparatus example that uses toner of the present invention is shown;

Figure 11 is the explanatory view that the full-colour image forming device example that adopts image forming method of the present invention is shown;

Figure 12 illustrates the explanatory view that is used for disintegrating apparatus system example of the present invention;

Figure 13 is the section of outline view along D-D ' face intercepting shown in Figure 12;

Figure 14 illustrates the explanatory view that is used for surface modification equipment system example of the present invention;

Figure 15 is the stripping curve with the soxhlet extraction of THF that is used for the toner of each embodiment 1 to 6; With

Figure 16 is the stripping curve with the soxhlet extraction of THF that is used for the toner of each embodiment 1 and comparative example 1 to 6.

Description of reference numerals:

The P transfer materials

1 Electrifier frame, photoreceptor

2 charging assemblies

3 exposure assemblies

4 developing devices

5 transfer printing assemblies

6 photographic fixing assemblies

7 cleaning assemblies

8 brush charging assemblies (brush charging assembly)

10 developing devices

12 photographic fixing assemblies

13 transfer belt

14 drive member

15 drive member

17 developer bearing members

19 transfer printing assemblies

30 main body covers

31 cooling jackets

32 dispersion rotors

More than 33 square plate

34 liners

35 classification rotors

36 guide rings

37 raw material input ports

38 raw material supplying valves

39 raw material supplying mouths

40 product escape holes

41 product exhaust valves

42 products extract mouth

43 top boards

44 fine powder discharge portions

45 fine powder escape holes

46 cold air intakes

47 first spaces

48 second spaces

49 surface modified area

50 graded regions

219 pipes

222 bag hoses (bag filter)

224 suction drum blower fans

229 collect cyclone separator (collection cyclone)

301 mechanical type comminutors

302 raw material escape holes

310 stators

311 raw material input ports

312 centre rotational axis

313 shells

314 rotors

315 quantitative feeder

316 chucks

319 cold air generation devices

320 cold water generation devices

321 toner-particle transfer devices

359 cyclone inlet

362 bags (bag)

364 fan blowers

369 cyclone separators

380 raw material hoppers

Embodiment

Hereinafter, will describe realization preferred forms of the present invention in detail.

At first, the physical property of toner of the present invention will be described in detail.

(physical property of toner)

Toner of the present invention comprises the toner-particle that comprises resin glue and colorant separately at least, wherein, when making described toner carry out soxhlet extraction in the time of 2 hours with THF, the tetrahydrofuran of the resin glue in toner (THF) insoluble substance is represented by A (quality %), when making described toner carry out soxhlet extraction in the time of 4 hours with THF, the THF insoluble substance of the resin glue in toner is represented by B (quality %), when making described toner carry out soxhlet extraction in the time of 8 hours with THF, the THF insoluble substance of the resin glue in toner is represented by C (quality %), and when making described toner carry out soxhlet extraction in the time of 16 hours with THF, under the situation of the THF insoluble substance of the resin glue in toner by D (quality %) expression, A, B, C and D satisfy following expression formula (1):

(A-B)/2>(B-C)/4>(C-D)/8 (1)

Wherein 40＜A≤75 (quality %) and 1.0＜D＜40 (quality %).

When these THF insoluble substances A, B, C and the D (quality %) of the resin glue in toner satisfy the relational expression of being represented by expression formula (1), as purpose of the present invention, even the toner that also can realize highly compatible extra between photographic fixing ability and the development capability in light compression set shadow system and rapid development system can be provided.Satisfy by the relational expression of above-mentioned expression formula (1) expression and wherein the photographic fixing ability of toner and the good zone of development capability are shown among Fig. 1 in the stripping curve in the soxhlet extraction (synoptic diagram).

At first, in the present invention, as shown in Figure 1, the relational expression that satisfies for the stripping curve in the soxhlet extraction by expression formula (1) expression is important.When stripping curve satisfies the relational expression of being represented by expression formula (1), resin glue in toner when photographic fixing in the quick stripping of low-temperature region, and the stripping in high-temperature area when photographic fixing of the resin glue in the toner is inhibited, and can guarantee good low temperature fixation performance and wide photographic fixing scope thus.

When stripping curve (when curve does not satisfy relational expression by expression formula (1) expression) when for example satisfying the curve by the relational expression of following formula (2) expression, resin glue in the toner when photographic fixing in the slow stripping of low-temperature region, and the resin glue in the toner is in the quick stripping of high-temperature area, and the result is that low-temperature fixing and photographic fixing scope all worsen.

(A-B)/2<(B-C)/4<(C-D)/8 (2)

In addition, when stripping curve is the straight line that does not satisfy by the relational expression of expression formula (1) expression, and when its gradient has big absolute value, resin glue in toner is in the quick stripping of low-temperature region, but resin glue is also in the quick stripping of high-temperature area, though the result obtains good low-temperature fixing, it is extremely narrow that the photographic fixing scope becomes.

On the contrary, when stripping curve is the straight line that does not satisfy by the relational expression of expression formula (1) expression, and when its gradient has little absolute value, resin glue in the toner is in the slow stripping of high-temperature area, but resin glue is at low-temperature region also slowly stripping, and the result is that the photographic fixing scope moves to high-temperature area.

As mentioned above, when the stripping curve of the resin glue in the toner satisfies the relational expression of being represented by expression formula (1), can give full play to effect of the present invention, so that guarantee good low-temperature fixing and photographic fixing scope.In this low-temperature fixing system of energy saving excellence as mentioned above, aforementioned toner physical property is particularly preferred.

In addition, in the present invention, it is important satisfying the relational expression of being represented by expression formula (1) as shown in Figure 1 for the stripping curve in the soxhlet extraction, so that realize the highly compatible between photographic fixing ability and the development capability.In addition, in the case, can obtain to have the image of high gloss and high chroma for a long time.

When THF insoluble substance A (quality %) is 40 (quality %) when following, can obtain good low-temperature fixing, and the image with high gloss and high chroma, but toner is easy to worsen when rapid development, and developing member is easy to pollute.When THF insoluble substance A (quality %) surpassed 75 (quality %), even also can obtain good development capability when rapid development, but low-temperature fixing, glossiness and colourity were easy to deficiency.

In addition, when THF insoluble substance D (quality %) is 1.0 (quality %) when following, can obtain good low-temperature fixing, but hot stained phenomenon is easy to occur in the high-temperature area.When THF insoluble substance D (quality %) is 40 (quality %) when above, can obtain good hot stained property, but low-temperature fixing is easy to deficiency, and, producing by comminuting method under the situation of toner, the grindability of toner worsens, so throughput rate is easy to worsen.

As mentioned above, when the stripping curve in soxhlet extraction satisfies as shown in Figure 1 relational expression by expression formula (1) expression, can give full play to effect of the present invention, so that realize the highly compatible between photographic fixing ability and the development capability.Toner preferably has aforementioned physical property so that is adapted to aforesaid this light compression set shadow system and rapid development system especially.

Toner of the present invention preferably locates to have the highest endothermic peak at 50 to 110 ℃ in the endothermic curve in differential scanning calorimetry (DSC).

When the highest endothermic peak with toner is positioned at described scope, can obtains above-mentioned good fixation performance, and can promote the improvement of development capability.At first, additional improvement the separation property between fixing member and the toner, can prevent the generation that fixing member for example pollutes, can obtain good image for a long time thus.When using aforesaid light compression set shadow system especially under high temperature and high humidity, the fixing temperature at the fusing nip place distributes and the photographic fixing pressure distribution becomes inhomogeneous, so aggravates from the separation property of fixing member.Consider aforementionedly,, improved the demoulding effect of the toner in fusing nip,, can both improve separation property thus regardless of Temperature Distribution and pressure distribution when the highest endothermic peak with toner is positioned at 50 to 110 ℃ when locating.Be lower than 50 ℃ when locating when the highest endothermic peak with toner is positioned at, can obtain good separation property, but the bin stability of toner worsens, perhaps the pollution of the deterioration of toner or developing member becomes remarkable when rapid development.Be higher than 110 ℃ when locating when the highest endothermic peak with toner is positioned at, can not obtain good separation property, and recording materials twine around fixing member, or the pollution etc. of fixing member takes place in some cases.

Have the THF insoluble substance A, B, C and the D (quality %) that satisfy above-mentioned expression formula (1) toner can resin obtains by for example suitably regulating.In addition, have above-mentioned the highest endothermic peak by DSC toner can wax obtains by for example suitably regulating.

In addition, toner of the present invention preferably has 1.0 * 10 ³DN/m ²Below to being lower than 1.0 * 10 ⁵DN/m ²The storage elastic modulus G under 140 ℃ ' (140 ℃).

When the storage elastic modulus G of toner ' when (140 ℃) fall in the described scope, can obtain above-mentioned good photographic fixing ability, and can promote the improvement of development capability.When storage elastic modulus G ' (140 ℃) of toner are lower than 1.0 * 10 ³DN/m ²The time, can obtain good low-temperature fixing, this is because the viscosity of toner reduces, still the hot stained property of toner and bin stability become not enough in high-temperature area.In addition, the pollution of the deterioration of toner or developing member is easy to take place when rapid development.When storage elastic modulus G ' (140 ℃) of toner surpass 1.0 * 10 ⁵DN/m ²The time, can obtain good hot stained property, this is because the elasticity of toner increases, but low-temperature fixing is easy to deficiency, and under the situation that toner is produced by comminuting method, the grindability of toner worsens, so throughput rate is easy to worsen.

Should note, store elastic modulus G ' (140 ℃) and can satisfy above-mentioned condition: each low softening point resin that will describe after a while and composition, softening point and the molecular weight distribution of high softening point resin, the addition of crosslinked charge control agent when compounding ratio between the described resin and kneading resin glue by regulating following condition.

In addition, toner of the present invention preferably has more than 0.945 to the average circularity below 0.990, described average circularity is by following acquisition: more than 0.200 to the circularity scope below 1.000, will be that the circularity that the streaming particle image measurement mechanism of 512 * 512 pixels (every pixel 0.37 μ m * 0.37 μ m) is measured is divided into 800 parts and analyzes described circularity with having Flame Image Process resolution.

When the average circularity of toner falls in the described scope, can obtain above-mentioned good photographic fixing ability, and can promote the improvement of development capability.When the average circularity of toner was lower than 0.945, the frictional electrification of toner was easy to inhomogeneous, so development capability also is easy to deficiency, and transfer efficiency also is easy to deficiency.When the average circularity of toner surpasses 0.990, it is even that the frictional electrification of toner becomes, therefore can obtain good development capability and good transfer efficiency, but the flowability of toner uprises so that dispersing of toner etc. taken place when transfer printing, and it is for forming the reason of bad image sometimes.

The average circularity that it should be noted that toner can be by regulating the condition pulverized with the disintegrating apparatus of describing after a while and satisfying above-mentioned condition with the condition of the surface modification equipment modification of description after a while.

Next, the material that detailed description be can be used in toner of the present invention is formed.(material of toner is formed)

Can be used in resin glue of the present invention and can be any known resin; The resin that preferably will have polyester unit is as described resin glue.Example with resin of polyester unit comprises: (a) vibrin, (b) have the potpourri and (f) potpourri of vibrin, hybrid resin and vinyl-based copolymer of potpourri, (e) hybrid resin and vibrin of potpourri, (d) vibrin and vinyl-based copolymer of hybrid resin, (c) hybrid resin and the vinyl-based copolymer of polyester unit and vinyl-based copolymer unit.In these, preferred hybrid resin is so that can obtain effect of the present invention.

When with vibrin when the resin glue, can be with polyvalent alcohol and polybasic carboxylic acid, polybasic acid anhydride, multi-carboxylate etc. as starting monomer.In addition, be equally applicable in hybrid resin, will be used for the monomer of production polyester unit.

The instantiation of diol component comprises: the alkylene oxide adduct of bisphenol-A such as polyoxypropylene (2.2)-2, two (4-hydroxyphenyl) propane of 2-, polyoxypropylene (3.3)-2, two (4-hydroxyphenyl) propane of 2-, polyoxyethylene (2.0)-2, two (4-hydroxyphenyl) propane of 2-, polyoxypropylene (2.0)-polyoxyethylene (2.0)-2, two (4-hydroxyphenyl) propane of 2-and polyoxypropylene (6)-2, two (4-hydroxyphenyl) propane of 2-; Ethylene glycol, diglycol, triethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, neopentyl glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4 cyclohexane dimethanol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene glycol, bisphenol-A and hydrogenated bisphenol A.

Example with alkoxide component of three above hydroxyls comprises sorbierite, 1,2,3, the own tetrol of 6-, 1,4-anhydro sorbitol, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-penta triol, glycerine, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxy methyl benzene.

The example of dibasic acid component comprises: aromatic dicarboxylic acid such as phthalic acid, m-phthalic acid and terephthalic acid (TPA), and acid anhydrides; Alkyl dicarboxylic aid such as succinic acid, hexane diacid, decanedioic acid and azelaic acid, and acid anhydrides; By the succinic acid of alkyl replacement with 6 to 12 carbon atoms, and acid anhydrides; And unsaturated dicarboxylic such as fumaric acid, maleic acid and citraconic acid, and acid anhydrides.

In addition, the example that is used to form the polybasic carboxylic acid component of the vibrin with crosslink sites more than the ternary comprises 1,2,4-benzene tricarbonic acid, 1,2,5-benzene tricarbonic acid, 1,2,4-naphthalene tricarboxylic acids, 2,5,7-naphthalene tricarboxylic acids and 1,2,4,5-benzene tertacarbonic acid, and these sour acid anhydrides and ester compounds.

In these, especially, the preferred vibrin by following acquisition: the bisphenol derivative that has by with the structure of following formula (i) expression is formed as polyol component with by the carboxylic acid more than the divalence, or carrying out polycondensation as acid constituents by the carboxyl acid component that the acid anhydrides or the lower alkyl esters of this acid (as fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid (TPA), trimellitic acid or pyromellitic acid) are formed, this is because described resin has good charging property.

Wherein R represents ethylidene or propylidene, and x and y represent the integer more than 1 separately, and the mean value of x+y is 2 to 10.

" hybrid resin " as resin glue of sneaking in the toner of the present invention is meant vinyl class in polymer unit and the polyester unit resin of chemical bonding each other.Particularly, hybrid resin is the resin that forms by the ester exchange reaction between polyester unit and the vinyl class in polymer unit, and described vinyl class in polymer unit obtains by monomer such as the methacrylate that polymerization has carboxylic acid ester groups; Hybrid resin preferably uses vinyl class in polymer as trunk polymkeric substance and the polyester unit graft copolymer (or segmented copolymer) as branched polymers.It should be noted that as being used for term of the present invention " polyester unit " to be meant the part that is derived from polyester, be meant the part that is derived from vinyl class in polymer as being used for term of the present invention " vinyl class in polymer unit ".The polyesters monomer of forming polyester unit is polybasic carboxylic acid component and polyol component, and the vinyl class in polymer unit is the monomer component with vinyl groups.

The example that is used to produce the vinyl monomer of vinyl-based copolymer or vinyl class in polymer unit comprises: styrene; Styrene derivative such as o-methyl styrene, a methyl styrene, p-methylstyrene, α-Jia Jibenyixi, to styryl phenyl, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene, align dodecyl styrene, to methoxy styrene, to chlorostyrene, 3,4-dichlorostyrene, m-nitro ethene, ortho-nitrophenyl ethene and p-nitrophenyl ethene; Unsaturated mono-olefin such as ethene, propylene, butylene and isobutylene; Unsaturated polyene such as butadiene and isoprene; Halogen ethene such as vinyl chloride, vinylidene chloride, bromine ethene and fluorothene; Vinyl esters such as vinyl acetate, propionate and vinyl benzoate; Alpha-methylene aliphatic monocarboxylic acid ester such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid 2-Octyl Nitrite, methacrylic acid stearyl ester, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid n-octyl, dodecylacrylate, 2-EHA, stearyl acrylate ester, acrylic acid 2-chloroethene ester and phenyl acrylate; Vinyl ether such as vinyl methyl ether, EVE and vinyl isobutyl ether; Vinyl ketone such as ethenyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compound such as N-vinyl pyrrole, N-vinylcarbazole, N-vinyl indoles and N-vinyl pyrrolidone; Vinyl naphthalene; With acrylate or methacrylate derivative such as vinyl cyanide, methacrylonitrile and acrylamide.

In addition, unsaturated dibasic acid such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid and mesaconic acid; Unsaturated dibasic acid acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydrides; Unsaturated dibasic acid half ester such as maleic acid methyl esters half ester, ethyl maleate half ester, maleic acid butyl ester half ester, citraconic acid methyl esters half ester, citraconic acid ethyl ester half ester, citraconic acid butyl ester half ester, itaconic acid methyl esters half ester, alkenyl succinic methyl esters half ester, fumarate dimethyl half ester and mesaconic acid methyl esters half ester; Unsaturated dibasic acid ester such as dimethyl maleate and dimethyl fumarate; α, beta-unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, the acid anhydrides of beta-unsaturated acid such as crotonic anhydride and cinnamic anhydride; Above-mentioned α, the acid anhydrides of beta-unsaturated acid and lower fatty acid; And monomer such as alkenyl malonic acid, alkenyl glutaric acid and alkenyl hexane diacid and acid anhydrides and its monoesters with carboxyl.

In addition, acrylate or methacrylate such as acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid 2-hydroxy propyl ester; With the monomer with hydroxyl such as 4-(1-hydroxyl-1-methyl butyl) styrene and 4-(1-hydroxyl-1-methyl hexyl) styrene.

In toner of the present invention, the ethylenic copolymer of resin glue and polyvinyl unit can have and have the crosslinked cross-linked structure of crosslinking chemical of two above vinyl.

In the case, with the example of crosslinking chemical comprise: divinyl aromatic compound such as divinylbenzene and divinyl naphthalene; Diacrylate ester compounds with the alkyl chain bonding, as glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediyl ester, neopentylglycol diacrylate and by the acrylate of each above-claimed cpd being changed into those that methacrylate obtains; Diacrylate ester compounds with the alkyl chain bonding of ether-containing key, as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #400 diacrylate, polyglycol #600 diacrylate, propylene glycol diacrylate with by the acrylate of each above-claimed cpd being changed into those that methacrylate obtains; And with the diacrylate ester compounds of the chain bonding that contains aromatic group and ehter bond, as polyoxyethylene (2)-2, two (4-hydroxyphenyl) the propane diacrylates of 2-, polyoxyethylene (4)-2, two (4-hydroxyphenyl) the propane diacrylates of 2-, and by the acrylate of each above-claimed cpd being changed into those that methacrylate obtains.

The example of multifunctional crosslinking chemical comprises: pentaerythritol triacrylate, trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and by the acrylate of each above-claimed cpd being changed into those that methacrylate obtains; Triallyl cyanurate and triallyl trimellitate.

When making hybrid resin, preferred vinyl base polymer unit and polyester unit separately or both all comprise the monomer component that can all react with two kinds of resin blocking compounds.In forming the monomer component of polyester unit, can comprise unsaturated dicarboxylic such as fumaric acid, maleic acid, citraconic acid and itaconic acid with the example of the monomer component of vinyl class in polymer unit process, and acid anhydrides.In the monomer component of forming the vinyl class in polymer unit, can comprise compound, acrylate and methacrylate with the example of the monomer component of polyester unit reaction with carboxyl or hydroxyl.

The method for optimizing that obtains reaction product between vinyl class in polymer unit and the polyester unit comprises: comprise can with the polymkeric substance of each monomer component that all reacts in above-mentioned vinyl class in polymer unit and the polyester unit in the presence of, carry out the polyreaction of one or both resins.

The example that is used to produce the polymerization initiator of vinyl-based copolymer or vinyl class in polymer unit comprises 2; 2 '-azoisobutyronitrile; 2; 2 '-azo two (4-methoxyl-2; the 4-methyl pentane nitrile); 2; 2 '-azo two (2; the 4-methyl pentane nitrile); 2; 2 '-azo two (2-methylbutyronitrile); dimethyl-2; 2 '-azo-bis-iso-butyl; 1; 1 '-azo two (1-cyclohexanenitrile); 2-carbamyl azo isobutyronitrile; 2; 2 '-azo two (2; 4; the 4-trimethylpentane); 2-phenylazo-2; 4-dimethyl-4-methoxyl valeronitrile; 2; 2 '-azo two (2-methylpropane); ketone peroxide such as methyl ethyl ketone peroxide; diacetone peroxide and cyclohexanone peroxide; 2; 2-two (t-butylperoxy) butane; tert-butyl hydroperoxide; cumene hydroperoxide; 1; 1; 3; 3-tetramethyl butyl hydroperoxides; di-t-butyl peroxide; the tert-butyl peroxide cumyl; dicumyl peroxide; α; α '-two (tert-butyl hydroperoxide isopropyl) benzene; the peroxidating isobutyl; the peroxidating decoyl; decanoyl peroxide; lauroyl peroxide; peroxidating 3; 5, the 5-trimethyl acetyl; benzoyl peroxide; m-toluyl peroxide; diisopropyl is crossed two carbonic esters; two-2-ethylhexyl is crossed two carbonic esters; di is crossed two carbonic esters; two-2-ethoxyethyl group peroxocarbonate; the dimethoxy isopropyl is crossed two carbonic esters; two (3-methyl-3-methoxyl butyl) peroxocarbonate; acetyl peroxide cyclohexyl sulphonyl; tert-butyl peroxy acetate; tert-butyl peroxyisobutyrate; the peroxide neodecanoic acid tert-butyl ester; uncle's peroxide-2 ethyl hexanoic acid butyl ester; the peroxide lauric acid tert-butyl ester; t-butyl peroxybenzoate; BPIC (t butyl peroxy isopropyl carbonate); peroxide m-phthalic acid di tert butyl carbonate; the t-butyl peroxy allyl carbonate; peroxide-2 ethyl hexanoic acid tert-pentyl ester; peroxide six hydrogen terephthalic acids di tert butyl carbonates and peroxide azelaic acid di tert butyl carbonate.

The example of the method for the hybrid resin in the production toner of the present invention comprises the production method that is shown in following (1) to (5).

(1) method of production hybrid resin comprises: produce vinyl class in polymer and vibrin respectively; Make vinyl class in polymer and vibrin dissolving and swelling in a small amount of organic solvent; Add esterification catalyst and alcohol to described solution; And heat described potpourri to carry out ester exchange reaction.

(2) production has the method for the hybrid resin of vibrin component and vinyl-based resin Composition, comprising: at first produce vinyl class in polymer; In the presence of vinyl class in polymer, make the vibrin component reaction then.The hybrid resin component is by following production: vinyl class in polymer unit (if desired, can add vinyl monomer) and polyester monocase (polyvalent alcohol or polybasic carboxylic acid) are reacted or make said units and monomer and the pet reaction that needs interpolation.In the case, can use any suitable organic solvent.

(3) production has the method for the hybrid resin of vibrin component and vinyl-based resin Composition, comprising: produce vibrin; Then, in the presence of vibrin, make vinyl-based resin Composition reaction.The hybrid resin component is by following production: make polyester unit (if desired, can add polyester monocase) with the vinyl monomer reaction or make said units and monomer and the vinyl class in polymer unit process that needs adding.In the case, can use any suitable organic solvent.

(4) method of production hybrid resin component comprises: produce vinyl class in polymer and vibrin; Then in the presence of these polymer units, add each or both of vinyl monomer and polyester monocase (polyvalent alcohol or polybasic carboxylic acid); And under condition, carry out polymerization according to the monomer that adds.In the case, can use any suitable organic solvent.

(5) method of production vinyl class in polymer unit, polyester unit and hybrid resin component comprises: mixed ethylene base class monomer and polyester monocase (polyvalent alcohol or polybasic carboxylic acid); And carry out continuous polyaddition reaction and polycondensation reaction.In addition, can use any suitable organic solvent.

At aforementioned production method (1) in (5), for vinyl class in polymer unit and polyester unit, a plurality of polymer units that can use molecular weight or degree of crosslinking to differ from one another.

Should note, be meant vinyl-based homopolymer or vinyl-based copolymer as being used for term of the present invention " vinyl class in polymer ", be meant vinyl-based homopolymer unit or vinyl-based copolymer unit as being used for term of the present invention " vinyl class in polymer unit ".

Preferably aforesaid two or more these resin glues are used for toner of the present invention.About the physical property of resin glue, the resin glue that especially preferably uses softening point to differ from one another.

Be meant the 1/2 method temperature of measuring based on JISK 7210 usefulness koka type flow testers (koka type flow tester) as being used for term of the present invention " softening point ".To describe concrete measuring method in detail after a while.Preferably low softening point resin and high softening point resin are used as the resin glue that softening point differs from one another.Low softening point resin have preferred more than 80.0 ℃ to being lower than 110.0 ℃, or more preferably more than 80.0 ℃ to the softening point that is lower than 95.0 ℃.High softening point resin have preferred more than 110.0 ℃ to below 145.0 ℃, or more preferably more than 130.0 ℃ to the softening point below 145.0 ℃.In addition, low softening point resin and high softening point resin preferably comprise hybrid resin separately at least.Be used in combination aforesaid low softening point resin and high softening point resin and can accelerate the stripping of the resin glue in the toner in low-temperature region, and can postpone the stripping of the resin glue in the toner in high-temperature area.That is, can guarantee good low-temperature fixing and photographic fixing scope.

The condition of polymer resin satisfies above-mentioned condition when it should be noted that composition that the softening point of resin glue can be by regulating resin glue and polymerization.

The hybrid resin that can sneak into low softening point resin is this: the ratio of components of polyester unit and vinyl class in polymer unit (quantity of the quantity of polyester unit/vinyl class in polymer unit) is preferably 60/40 to 95/5, or more preferably 70/30 to 95/5 scope.The hybrid resin that can sneak into high softening point resin is this: the ratio of components of polyester unit and vinyl class in polymer unit (quantity of the quantity of polyester unit/vinyl class in polymer unit) is preferably 50/50 to 90/10, or more preferably 60/40 to 90/10 scope.In addition, the ratio of components of the polyester unit of low softening point resin is preferably greater than the ratio of components of the polyester unit of high softening point resin.This is because the efficient of improvement low-temperature fixing increases with the increase of the ratio of components of the polyester unit in the low softening point resin.Unclear for aforesaid reason, but a possible reason is as follows: when low softening point resin and high softening point resin have identical composition, compatibility between two kinds of resin glues becomes good, and two kinds of resin glues in the toner are disperseed in ultra-fine mode, so resin can not be in above-mentioned low-temperature region and high-temperature area be shared on the basis in function and is worked.

In addition, can be used in low softening point resin in the toner of the present invention and the compounding between the high softening point resin than (quality of the quality/high softening point resin of low softening point resin) preferably in 50/50 to 90/10 scope.This is because compare greater than 1/1 the time when the compounding of low softening point resin and high softening point resin, can easily be controlled at the stripping of the resin glue in the toner in the low-temperature region.

Can be used in low softening point resin of the present invention in the molecular weight distribution of measuring by gel permeation chromatography (GPC) at 1,000 to 10,000 molecular weight region, or more preferably have main peak in 2,000 to 6,000 the molecular weight region.In addition, the ratio of the number-average molecular weight (Mn) of the weight-average molecular weight of low softening point resin (Mw) and this resin preferred more than 2.0 to below 40.

Be lower than when low softening point resin when having main peak in 1,000 the molecular weight region, the bin stability of toner aggravates.On the other hand, when low softening point resin is surpassing when having main peak in 10,000 the molecular weight region, the low-temperature fixing of toner, glossiness and colourity are tending towards reducing so that are not enough.In addition, when the ratio Mw/Mn of low softening point resin was lower than 2.0, the bin stability of toner aggravated.When the ratio Mw/Mn of low softening point resin surpassed 40, toner can not obtain sufficient low-temperature fixing.

In addition, can be used in high softening point resin of the present invention in the molecular weight distribution of measuring by gel permeation chromatography (GPC) at 5,000 to 15,000 molecular weight region, or more preferably have main peak in 6,000 to 12,000 the molecular weight region.In addition, the ratio of the number-average molecular weight (Mn) of the weight-average molecular weight of high softening point resin (Mw) and this resin preferred more than 40 to below 400.

Be lower than when high softening point resin when having main peak in 5,000 the molecular weight region, the hot stained property of toner aggravates.On the other hand, when high softening point resin is surpassing when having main peak in 15,000 the molecular weight region, the low-temperature fixing of toner, glossiness and colourity are tending towards reducing so that are not enough.In addition, when the ratio Mw/Mn of high softening point resin was lower than 40, the hot stained property of toner aggravated.When the ratio Mw/Mn of high softening point resin surpassed 400, the glossiness of toner and colourity can reduce so that is not enough.

In addition, when toner of the present invention was used for not having the oilless fixing unit of oil-filling mechanism, from improving the viewpoint of photographic fixing ability, toner preferably comprised wax as release agent.

The example that can be used in wax of the present invention comprises following: aliphatic chloroflo such as low molecular weight polyethylene, low-molecular-weight polypropylene, olefin copolymer, microcrystalline wax, paraffin and Fischer-Tropsch (Fischer-Tropsch) wax; The segmented copolymer of aliphatic series chloroflo oxide such as polyethylene oxide wax or aliphatic chloroflo; Comprise wax such as Brazil wax, behenic acid Shan Yu ester and the brown coal ester type waxes of aliphatic (acid) ester as key component; And the wax such as the deoxidation Brazil wax that comprise the aliphatic (acid) ester of part or all of deoxidation.In addition, the example of wax comprises: linear saturated fatty acids such as palmitic acid, stearic acid and montanic acid; Unsaturated fatty acid such as brassidic acid, eleostearic acid and parinaric acid (barinarin acid); Saturated alcohols such as stearyl alcohol, aralkyl alcohol, tadenan, tetracosanol, the pure and mild triacontanol of hexacosane; Polyvalent alcohol is sorbierite for example; Fatty acid such as palmitic acid, stearic acid, behenic acid and montanic acid and alcohol are as the ester of stearyl alcohol, aralkyl alcohol, tadenan, tetracosanol, the pure and mild triacontanol of hexacosane; Fatty acid amide is linoleic acid acid amides, oleamide and lauramide for example; The saturated fat bisamide is di-2-ethylhexylphosphine oxide stearmide, ethylenebis decyl amide, ethylenebis lauroyl ammonium and hexa-methylene bis-stearamides for example; The unsaturated fat acid amides is ethylenebisoleaamide, the two oleamides of hexa-methylene, N for example, N '-two oil base adipamide and N, N '-two oil base decyl amide; The fragrance bisamide is m-xylene bis-stearamides and N for example, the N '-different phthalamide of distearyl acyl group; Fatty acid metal salts (alleged metallic soap usually) is calcium stearate, calcium laurate, zinc stearate and dolomol for example; Wherein with vinyl monomer for example styrene and acrylic acid with the grafting wax of fatty chloroflo grafting; The compound of the partial esterification of fatty acid and polyvalent alcohol is the behenic acid monoglyceride for example; The methyl-esterified compound that obtains with hydrogenation with hydroxyl by vegetable oil.

The example that can be particularly preferred for wax of the present invention comprises aliphatic hydrocarbon wax and as the esterification compound of the ester of fatty acid and alcohol.Aforesaid expectation example comprises: by the low molecular weight olefin polymerization thing of following acquisition: under high pressure make alkene carry out free radical polymerization or by using Ziegler (Ziegler) catalyzer or metalloscene catalyst olefin polymerization under reduced pressure; Olefin polymer by the acquisition of thermal decomposition high molecular weight olefin polymkeric substance; And the synthetic chloroflo that obtains by residue when hydrocarbon distills, described hydrocarbon obtains and synthetic chloroflo by this gas hydrogenation acquisition from the forming gas that contains carbon monoxide and hydrogen by aging (Age) method.In addition, more preferably use the product that pressurizes diaphoresis, solvent method, utilizes vacuum distillation or fractional crystallization pattern to obtain by employing by this chloroflo of fractionation.Preferably following hydrocarbon is used as hydrocarbon: use metal oxide-type catalyzer (many body system of forming by two or more elements in many cases) by the synthetic hydrocarbon of the reaction between carbon monoxide and the hydrogen [for example helping stream to help the synthetic hydrocarbon compound of filter (hydrocol) method (comprise and use the fluid catalyst bed)] by synthol process or particulate as this aliphatic chloroflo parent, has a hydrocarbon (comprising the use stationary catalyst bed) that reaches a hundreds of carbon atom by what the aging process that can obtain a large amount of wax shape hydrocarbon obtained, or the hydrocarbon by using Zeigler catalyst to obtain by olefin polymerization such as ethene, this is because every kind of hydrocarbon all is have the minority branchlet saturated, long, straight chain hydrocarbon.The preferred especially synthetic wax of method by not comprising olefin polymerization, this is because its molecular weight distribution.Also preferably use paraffin.

In addition, toner of the present invention preferably locates to have the highest endothermic peak at 50 to 110 ℃ in 30 to 200 ℃ temperature range in the endothermic curve of differential scanning calorimetry (DSC).When the highest endothermic peak is positioned at the following time of temperature that is lower than 50 ℃, the bin stability of toner aggravates.On the contrary, surpass 110 ℃ following time of temperature when the highest endothermic peak is positioned at, the photographic fixing ability of toner aggravates.

In addition, preferably will can be used in wax of the present invention and be converted into masterbatch as dispersing agent for wax.

Especially preferably with (i) vibrin, (ii) wax and (iii) multipolymer be used for dispersing agent for wax, described multipolymer has at least by using styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, containing the synthetic multipolymer and the polyolefin of monomer of carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers.

Because it was originally low to can be used in the compatibility that has the resin glue of polyester unit and can be used between the hydrocarbon wax of the present invention of the present invention, so add when resin and wax are maintained the original state when being converted into toner, wax segregation in toner, the wax that generation is separated out etc.As a result, the pollution of the deterioration of toner and developing member is easy to take place during rapid development.

Consider aforementioned, resin combination is by will (ii) wax is finely divided in (iii) producing in the multipolymer, and described multipolymer obtains in the following manner: will be by using styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, containing the synthetic multipolymer and the polyolefin grafting of monomer of carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers.With resin combination as dispersing agent for wax, and with dispersing agent for wax as masterbatch fusion and mixing in (i) vibrin, so that obtain " dispersing agent for wax masterbatch ".Preferably when producing, toner adds and use dispersing agent for wax masterbatch.

Can be used for comprising following by the example of monomer that uses polystyrene type monomer and at least a vinyl monomer that is selected from nitrogen atom, contains the monomer synthetic copolymer of carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers.

Styrene monomer comprises, for example: phenylethylene such as styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene, to styryl phenyl, to chlorostyrene, 3, the 4-dichlorostyrene, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene and align dodecyl styrene; And derivant.

The example of the vinyl monomer of nitrogen atom comprises: contain amino acid whose alpha-methylene aliphatic monocarboxylic acid ester such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; And the derivant of acrylic or methacrylic acid such as vinyl cyanide, methacrylonitrile and acrylamide.

The example that contains carboxylic monomer comprises: unsaturated dibasic acid such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid and mesaconic acid; Unsaturated dibasic acid acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydrides; Unsaturated dibasic acid half ester such as maleic acid methyl esters half ester, ethyl maleate half ester, maleic acid butyl ester half ester, citraconic acid methyl esters half ester, citraconic acid ethyl ester half ester, citraconic acid butyl ester half ester, itaconic acid methyl esters half ester, alkenyl succinic methyl esters half ester, fumarate dimethyl half ester and mesaconic acid methyl esters half ester; Unsaturated dibasic acid ester such as dimethyl maleate and dimethyl fumarate; α, beta-unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, the acid anhydrides of beta-unsaturated acid such as crotonic anhydride and cinnamic anhydride, and above-mentioned α, the acid anhydrides of beta-unsaturated acid and lower fatty acid; And alkenyl malonic acid, alkenyl glutaric acid and alkenyl hexane diacid, and acid anhydrides and its monoesters.

The example of hydroxyl monomer comprises: acrylate or methacrylate such as acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate and methacrylic acid 2-hydroxy propyl ester; And 4-(1-hydroxyl-1-methyl butyl) styrene and 4-(1-hydroxyl-1-methyl hexyl) styrene.

The example of acrylate monomer comprises acrylate such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic acid n-octyl, dodecylacrylate, 2-EHA, stearyl acrylate ester, acrylic acid 2-chloroethene ester and phenyl acrylate.

The example of methacrylic acid monomer comprises alpha-methylene aliphatic monocarboxylic acid ester such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, n-BMA, isobutyl methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid 2-Octyl Nitrite, methacrylic acid stearyl ester, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

In these, the terpolymer of especially preferably forming by styrene, vinyl cyanide and butyl acrylate.

By using styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, containing in the molecular weight distribution of passing through GPC of the synthetic multipolymer of the monomer of carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers, weight-average molecular weight (Mw) is desirably in 5,000 to 100, in 000 the scope, number-average molecular weight (Mn) is desirably in 1,500 to 15, in 000 the scope, and the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is desirably in 2 to 40 the scope.

Be lower than 5 when having by the synthetic multipolymer of monomer that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers, 000 weight-average molecular weight (Mw), have and be lower than 1,500 number-average molecular weight (Mn), or the ratio (Mw/Mn) with weight-average molecular weight (Mw) and number-average molecular weight (Mn) is lower than at 2 o'clock, and the bin stability of toner significantly weakens.

When by using styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contain carboxylic monomer, the hydroxyl monomer, the synthetic multipolymer of the monomer of acrylate monomer and methacrylate monomers has above 100,000 weight-average molecular weight (Mw), have and surpass 15,000 number-average molecular weight (Mn), or the ratio (Mw/Mn) with weight-average molecular weight (Mw) and number-average molecular weight (Mn) was above 40 o'clock, finely divided wax in dispersing agent for wax can not promptly migrate to the surface of fusion toner when photographic fixing and fusion, therefore can not obtain the good separation as toner effect of the present invention.

In addition, be preferably 0.1 to 20 quality % by the synthetic content of multipolymer in toner of monomer that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers, based on the quality of toner.

When quality based on toner of the present invention, when surpassing 20 quality %, can weaken the low-temperature fixing of toner by the content that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains the synthetic multipolymer of the monomer of carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers.In addition, when described content is lower than 0.1 quality %, can reduce dispersion effect to wax.

Endothermic curve when being used for polyolefin with the multipolymer graft polymerization and being desirably in intensification by dsc measurement locates to have the highest endothermic peak at 90 to 130 ℃, and described multipolymer is synthetic by the monomer that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers.

When the highest polyolefinic endothermic peak is being lower than 90 ℃ or surpass 130 ℃ when locating to show local maximum, apparatus derivatorius in the graft copolymer of polyolefin and multipolymer is destroyed, described multipolymer is synthetic by the monomer that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers, therefore wax does not have finely divided, wax segregation when producing toner, and bad development is easy to take place.

The polyolefin of sneaking in the dispersing agent for wax of the present invention preferably has 500 to 30 in by the molecular weight distribution of GPC, 000 weight-average molecular weight (Mw), 500 to 3,000 number-average molecular weight (Mn), and the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.0 to 20, and preferably has 0.9 to 0.95 density.

When having, polyolefin is lower than 500 weight-average molecular weight (Mw), have and be lower than 500 number-average molecular weight (Mn), ratio (Mw/Mn) with weight-average molecular weight (Mw) and number-average molecular weight (Mn) is lower than 1.0, have and surpass 30,000 weight-average molecular weight (Mw), have and surpass 3,000 number-average molecular weight (Mn), or the ratio (Mw/Mn) with weight-average molecular weight (Mw) and number-average molecular weight (Mn) was above 20 o'clock, be difficult to obtain for improvement effect separatory, this is the surface that oozes out into toner because of finely divided wax in dispersing agent for wax when photographic fixing not yet in effectly.In addition, when polyolefin has when surpassing 0.95 density (polyolefinic density is not low), effective apparatus derivatorius in the graft copolymer of polyolefin and multipolymer is destroyed, described multipolymer by use styrene monomer and at least aly be selected from the nitrogen atom vinyl monomer, contain carboxylic monomer, the monomer of hydroxyl monomer, acrylate monomer and methacrylate monomers is synthetic, therefore wax segregation when producing toner, and bad development is easy to take place.

In addition, preferred 0.1 to the 2 quality % of the content of polyolefin in toner is based on the quality of toner.

When polyolefinic content surpasses 2 quality % based on the quality of toner, as under the situation of The above results, effective apparatus derivatorius in the graft copolymer of polyolefin and multipolymer is destroyed, described multipolymer is synthetic by the monomer that uses styrene monomer and at least a vinyl monomer that is selected from nitrogen atom, contains carboxylic monomer, hydroxyl monomer, acrylate monomer and methacrylate monomers, therefore wax does not have finely divided, wax segregation when producing toner, and poor visualization is easy to take place.In addition, when described content is lower than 0.1 quality %, can reduce dispersion effect to wax.

With at least a known dye and/or known pigment as the colorant in the toner of the present invention.

As pinkish red toner pigment, can be exemplified as color lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, perylene compound of condensation azo-compound, Diketopyrrolo-pyrrole compounds, anthraquinone, quinacridone compound, basic-dyeable fibre etc.Its instantiation comprises: C.I. paratonere 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31,32,37,38,39,40,41,48:2,48:3,48:4,49,50,51,52,53,54,55,57:1,58,60,63,64,68,81:1,83,87,88,89,90,112,114,122,123,144,146,150,163,166,169,177,184,185,202,206,207,209,220,221 and 254; C.I. pigment violet 19; With C.I. pigment urn red 1,2,10,13,15,23,29 and 35.

The example of pinkish red toner dyestuff comprises: oil-soluble dyes such as C.I. solvent red 1,3,8,23,24,25,27,30,49,81,82,83,84,100,109 and 121, C.I. disperse red 9, C.I. solvent purple 8,13,14,21 and 27 and C.I. disperse violet 1; And basic-dyeable fibre such as C.I. alkali red 1:1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39 and 40 and C.I. alkaline purple 1,3,7,10,14,15,21,25,26,27 and 28.

The example of cyan toner pigment comprises: C.I. pigment blue 1,2,3,7,15:2,15:3,15:4,16,17,60,62 and 66; C.I. vat blue 6; C.I. acid blue 45; With phthalocyanine frame is had as the methyl substituted copper phthalocyanine of phthalimide with the structure of following formula shown in (ii) with 1 to 5.

As yellow uitramarine, can be exemplified as condensation azo-compound, isoindoline ketonic compound, anthraquinone compounds, azo metal compound, methylidyne compound or allyl acid amides (allylamide) compound.Its instantiation comprises C.I. pigment yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,62,65,73,74,83,93,95,97,109,110,111,120,127,128,129,147,155,168,174,180,181,185 and 191; With C.I. vat yellow 1,3 and 20.In addition, also dyestuff such as C.I. direct green 6, C.I. Viride Nitens 4, C.I. Viride Nitens 6 and solvent yellow 16 2 can be used as colorant.

The example that can be used for black colorant of the present invention comprises carbon black, ferric oxide particles and by using above-mentioned Huang/magenta/cyan colorant to mix colours to the colorant with black.

Consider colorrendering quality and development capability, with colorant based in 100 mass parts resin glues preferably with 0.1 to 20 mass parts, or more preferably the amount of 1.0 to 16 mass parts is used for toner.

In addition, in toner of the present invention, the preferred masterbatch that obtains by in advance resin glue being mixed with colorant that uses.In addition, colorant advantageously can be scattered in the toner with other raw material (as resin glue and wax) by fusion and kneading colorant masterbatch.

When using resin glue and colorant to obtain masterbatch, improved the character that colorant is scattered in the toner to be had, and can obtain to have the image of high chroma.In addition, when forming image by the multi-color toner photographic fixing, it is excellent that colorrendering quality such as colour mixture or the transparency become.

Preferably will be suitable for this binder resin for toner of the present invention as mentioned above with acting on the resin glue that the colorant that will be used for toner of the present invention is converted into masterbatch.To have preferred more than 90.0 ℃ to below 130.0 ℃ (more preferably more than 95.0 ℃ to below 120.0 ℃, or also more preferably more than 100 ℃ to below 120 ℃) resin glue that will use when producing masterbatch of the middle softening point resin of softening point.In addition, middle softening point resin further preferably comprises hybrid resin at least.When being used in combination low softening point resin and high softening point resin as the resin glue in the toner of the present invention, when producing masterbatch will with middle softening point resin preferably have above the softening point of low softening point resin and be lower than the softening point of the softening point of high softening point resin, this is because the character that colorant is scattered in the toner to be had becomes good.When producing masterbatch will with the softening point of middle softening point resin be the softening point that is equal to or less than low softening point resin, or be when being equal to or higher than the softening point of high softening point resin, the character that colorant is scattered in the toner to be had worsens, and therefore can not obtain to have the image of high chroma.In addition, when forming image by the multi-color toner photographic fixing, colorrendering quality such as colour mixture or the transparency worsen in some cases.

Be used for making softening point resin that the colorant that will be used for toner of the present invention is converted into masterbatch in the molecular weight distribution of measuring by gel permeation chromatography (GPC) 1,000 to 14, in 000 the molecular weight region, or more preferably 2,000 to 11, have main peak in 000 the molecular weight region, and preferably have more than 2.0 to the ratio Mw/Mn below 40.

When main peak is positioned at when being lower than in 1,000 the molecular weight region, the bin stability of toner aggravates.On the other hand, when main peak is positioned at when surpassing in 14,000 the molecular weight region, the low-temperature fixing of toner, glossiness and colourity are tending towards reducing.In addition, Mw/Mn is lower than 2.0 when ratio, or surpasses at 40 o'clock, and the character that colorant is scattered in the toner to be had aggravates.

In addition, when producing masterbatch, can use the fusion that to describe after a while and the step of mediating toner by the colorant of toner of the present invention.In addition, masterbatch of the present invention comprises preferred 2 to 25 quality %, and more preferably 3 to 20 quality %, or the more preferably moisture of 5 to 18 quality % also are based on the total amount of colorant.With this moisture masterbatch (hereinafter can be referred to as " moisture MB "), can colorant is finely divided equably in toner.Unclear for previous reasons, but possible reason is as described below.

First cause is as described below.Comprise the raw material for toner potpourri of resin glue and moisture MB to provide second to mediate in the step (second fusion and kneading step) of product in fusion and kneading, moisture MB comprises big water gaging, so the existence of water has prevented the gathering of coloring agent particle between the coloring agent particle.In addition, the moisture that infiltrates through in the aggregation that is present in the coloring agent particle in a certain partially mixed thing expands so that aggregation subsides by means of the heat in second fusion and kneading step, thus particle is successfully disperseed.

Second reason is as described below.Second temperature of mediating product uprises, this be because: when second fusion and kneading step, as the heating certainly of the result's of the strong shearing that puts on the raw material for toner potpourri moisture MB; With as the basis that needs on from external heating.Yet water has been captured the heat as heat of evaporation when evaporation, therefore can prevent because the strong adhesion and the gathering of the toner-particle that thermal conductance causes.

The 3rd reason is as described below.As the result who produces steam when second fusion and the kneading step, because second mediate the expansion of product, apply strong shearing by the pressure that is increased in the kneader, produce extra strong shearing force thus.Described power is extremely effective in all components that disperses to comprise the coloring agent particle that is present in the second kneading product.

The liquid water content that can be used in moisture MB of the present invention is not preferred above 25 quality %, this is because because excessive liquid water content causes the bounding force of moisture MB so strong, so that MB is fused to process units such as Han Xieer (Henschel) mixer, or in some cases because mobile the reduction causes producing big aggregation in the raw material for toner potpourri.The liquid water content that is lower than 2 quality % also is not preferred, this is because the above-mentioned effect of expectability not, and the coloring agent particle that disperses in heating and drying steps under normal pressure or decompression is assembled the traces of moisture that is retained in the masterbatch to remove consumingly, therefore at subsequently the kneading step that toner is produced that is used for, becoming is difficult to advantageously be scattered here and there once more toner.

Known charge control agent can be used for toner of the present invention with the charging property of when mediating, stablizing toner and crosslinked with resin glue.Usually with charge control agent based on 100 mass parts resin glues with preferred 0.1 to 10 mass parts, or more preferably the amount of 0.1 to 5 mass parts is sneaked in the toner-particle, though described amount depend on the kind of charge control agent for example and form toner-particle other material physical property and change.The known embodiment of this charge control agent comprises that to be used to control toner be the charge control agent of negative charging and is used to control the charge control agent that toner is a Positively chargeable.Depend on the kind of toner and purposes and can use at least a in the various charge control agents.In addition, the charge control agent of some kinds can not only be controlled charging property but also cross-linked binder resin.

The example of available negative charge controlling agent comprises: salicylic metallic compound; The metallic compound of naphthoic acid; The metallic compound of dicarboxylic acid; The polymer compound that on its arbitrary side chain, has sulfonic acid or carboxylic acid separately; Boron compound; Carbamide compound; Silicon compound; And calixarenes.The example of available positive charge control agent comprises: quaternary ammonium salt; The polymer compound that on their side chain, has quaternary ammonium salt; Guanidine compound; And imidazolium compounds.Each of these charge control agents can inside or the outside be added in the toner-particle.

Especially, the metallic compound of aromatic carboxylic acid is for preferably can be used in the charge control agent of toner, the metallic compound of described aromatic carboxylic acid be colourless and can: under high speed, make toner of the present invention charged; Stably keep constant carried charge; With when mediating and resin glue crosslinked.The more preferably aluminium compound of aromatic carboxylic acid.

Before using toner of the present invention, the flowability of toner preferably by pulverize and classification after or regulate with mixer such as Han Xieer mixer mixing fine inorganic particles after the surface modification.

The example that can be used in inorganic powder of the present invention comprises: fluorine-type resin powder such as vinylidene fluoride (fluorinated vinylidene) fine powder and fine polytetrafluoroethylpowder powder; Titanium oxide fine powder; Aluminum oxide fine powder; Fine silica such as wet method silicon dioxide (wetprocess silica) and dry method silicon dioxide (dry process silica); Silane compound and their organo-silicon compound; And the surface is by the processing silicon dioxide of titanium coupling agent or silicone oil processing.In these, especially preferably use wet method silicon dioxide, dry method silicon dioxide, titanium oxide fine powder and aluminum oxide fine powder.

The instantiation of the silicon dioxide that obtains by wet method comprises: the silica dioxide granule of being produced by silicon dioxide gel suspending liquid, it is by following acquisition: desolventize by comprising, dry residue and desciccate is converted into the sol-gel process of particle, alkoxy silane is hydrolyzed and condensation reaction with catalyzer in water-containing organic solvent.Preferably by the silica dioxide granule of sol-gel process production, this is narrow because of the particle grain size distribution that obtains, because can obtain spheric grain and because can have the particle of expecting size distribution by changing the reaction time acquisition.

In addition, therefore the fine powder of silicon dioxide for producing by the gaseous oxidation halogenated silicon compound by dry method obtains be called dry method silicon dioxide or fumed silica.Dry method silicon dioxide or fumed silica are by conventional known technology production.For example, this produces the thermal decomposition oxidation reaction of utilizing in the oxyhydrogen flame of silicon tetrachloride gas, and the fundamental reaction formula of this reaction is expressed from the next:

SiCl ₄+2H ₂+O2→SiO ₂+4HCl

The composite fine powders of silicon dioxide and any other metal oxide also can obtain by use halogenated silicon compound and any other metal halide such as aluminum chloride or titanium chloride in production stage, and dry method silicon dioxide comprises composite fine powders equally.

In addition, can use by the following method the titanium oxide fine particle that obtains as titanium oxide fine powder: the sulfonic acid method; The chlorine method; And the low-temperature oxidation (thermal decomposition or hydrolysis) of volatile titanium compound such as titanium alkoxide (titanium alkoxide), halogenated titanium and acetylacetonate titanium.Can use any of the crystal system that comprises Detitanium-ore-type, rutile-type, their mixed crystal and amorphous type.

In addition, also can use by the following method the aluminum oxide fine powder that obtains as aluminum oxide fine powder: spark-discharge method, organo-aluminium Hydrolyze method, aluminium alum pyrolysismethod, aluminium carbonate ammonium pyrolysismethod or aluminum chloride flame decomposition method in Baeyer (Bayer) method, improved Baeyer (Bayer) method, chlorohydrin method, the water.Use comprises α, β, γ, δ, ξ, η, θ, κ, χ and ρ type, the crystal system of their mixed crystal and amorphous type any; Preferred α, δ, γ or θ type, their mixed crystal or the amorphous type of using.

By with for example with inorganic fine powder reaction or physisorption to the organo-silicon compound chemistry of inorganic fine powder or physically handle inorganic fine powder, give the inorganic fine powder hydrophobicity.Method for optimizing comprises with organo-silicon compound handles the fine silica of producing by the gaseous oxidation halogenated silicon compound.The example of these organo-silicon compound comprises hexamethyldisilazane, trimethyl silane, trimethyl chlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, the allyl phenyl dichlorosilane, the benzyl dimethyl chlorosilane, the bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, ρ-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silyl mercaptan, three Organosilyl acrylate, vinyl-dimethyl base acetoxylsilane, dimethylethoxysilane, dimethyldimethoxysil,ne, the diphenyl diethoxy silane, HMDO, 1, the 3-divinyl tetramethyl disiloxane, 1, have 2 to 12 siloxane units in 3-diphenyl tetramethyl disiloxane and the per molecule and comprise the dimethyl polysiloxane that is bonded to the hydroxyl on the silicon that is positioned at each end group unit.Can use a kind of in these compounds separately or use its two or more potpourri.

Can use above-mentioned usefulness to have wet method silicon dioxide that amino coupling agent or silicone oil handles or dry method silicon dioxide fine inorganic particles as the fluidizing agent that is used to realize that purpose of the present invention is required.In addition, with 0.01 to 8 mass parts, or the amount of preferred 0.1 to 4 mass parts adds with fluidizing agent in expectation, based on 100 mass parts toners.

Next, use description to produce the step of toner of the present invention.

(producing the method for toner)

Toner of the present invention is preferably by following production: fusion and kneading resin glue, colorant and any materials; Product is mediated in cooling; Pulverize cooled product; As required the product of pulverizing is carried out spheroidising or classification processing; And as required gains are mixed with fluidizing agent.

At first, in the raw material blend step, weighing, blend and mixing are as the resin at least and the colorant of the scheduled volume of toner internal additives.The example of mixing arrangement comprises Doublecon mixer, V-Mixer, drum type mixer, Super mixer, Han Xieer mixer, Q type mixer and Nuo Ta (Nauta) mixer.

In addition, will be in above-mentioned steps blend and mixing the raw material for toner fusion and mediate with bond vitrified agent resin, then colorant etc. is dispensed in the gains.In fusion and kneading step, can use batch-type kneader such as pressure kneader or Banbury (Banbury) mixer, or continuous kneader.In addition, single shaft or biaxial extruder have become main flow, and this is to carry out the quantity-produced ability because of its advantage such as its.For example, usually use by the PCM type biaxial extruder of Ikegai Corp. manufacturing, by KobeSteel, Ltd. the KTK type biaxial extruder of Zhi Zaoing, by Toshiba Machine Co., Ltd. the TEM type biaxial extruder of Zhi Zaoing, by KCK Co., Ltd. the biaxial extruder of Zhi Zaoing or by Bus Co., the coextrusion machine that Ltd. makes.In addition, will be by fusion and mediate colored resin composition that raw material for toner obtains in fusion with mediate the back by roll-ins such as two rollers, and water etc. cools off by cooling step.

Preferably in the raw materials melt and the kneading that will be used for toner of the present invention more than 90 ℃ to the kneading temperature below 150 ℃.The term of Shi Yonging " kneading temperature " is meant the temperature of colored resin composition when composition is extruded from extruder herein, and described composition obtains by fusion and kneading raw material for toner.The kneading temperature that is lower than 90 ℃ is not preferred, and this is because the raw material in toner is easy to disperse unfriendly.The kneading temperature that surpasses 150 ℃ is not preferred, this be because, when being used in combination low softening point resin and high softening point resin, compatibility between two kinds of adhesive resins improves, and two kinds of resin glues that are expected in the toner disperse in ultra-fine mode, and therefore becoming is difficult to obtain the physical property of toner of the present invention.

Next, the cooled product of the colored resin composition that will obtain in aforementioned is pulverized in pulverising step to having the expectation size particles separately.In pulverising step, at first with cooled product disintegrating machine, hammer-mill, the coarse crushings such as (feather mill) of pinniform muller, and further in small, broken bits with known air comminutor or mechanical type comminutor.In pulverising step, cooled product is pulverized to having predetermined toner size particles separately thus in mode progressively.In addition, gained product in small, broken bits can be carried out surface modification, that is, the spheroidization in the surface modification step is handled, so that obtain surface modified granules.Afterwards, with surface modified granules with for example following grader classification: according to the Elbow jet of inertial classification pattern (by Nittetsu Mining Co., Ltd. make), according to the Turboplex (making) of centrifugal classification pattern by Hosokawa Micron Corporation, or as required, the sieve classification machine is as the Hi-bolter (being made by Shin Tokyo KikaiKK) as the air sieve, and acquisition has the toner of the weight average particle diameter of 3 to 11 μ m thus.

It should be noted that the toner meal that will produce as classification results carries out classification step once more to pulverize in classification step.In addition, make step that the fine powder of producing in the surface modification step preferably carries out the blend raw material for toner with according to the recycle of toner throughput rate.

In addition, in the method for producing toner of the present invention, preferably will be used for giving mobile fine inorganic particles and be added into the toner that obtains as mentioned above as the external additive outside.Outside interpolation external additive to the method for optimizing of toner comprises: with the branch grade toner and the blend each other of various known external additives of scheduled volume; And be used to apply shearing force to homo-mixer such as Han Xieer mixer, Super mixer or the Q type mixer of powder stirred and mixed blend as outside adding machine product by use.In the case, externally therefore generation heat in the adding machine be easy to produce aggregation, so the temperature around the container portions of outside adding machine is preferably passed through as water-cooled method is regulated.

Toner of the present invention have preferred more than 0.945 to below 0.990, or more preferably more than 0.950 to the average circularity below 0.990.The average circularity of toner is measured with FPIA3000 (being made by SYSMEX CORPORATION), uses description to the method for measuring after a while.When the average circularity of toner falls in this scope, can obtain following advantage:, and improve the transfer printing ability even when rapid development, also can obtain good development capability.

Hereinafter, description is preferred for obtain being suitable for the mechanical type comminutor and the surface modification equipment of the average circularity of toner of the present invention.

When producing toner of the present invention, in pulverising step, preferably use the mechanical type comminutor as disintegrating apparatus.Figure 12 illustrates and is used to have the example that the toner-particle that can be used in built-in mechanical type comminutor of the present invention is used the disintegrating apparatus system.

Mechanical type comminutor 301 shown in Figure 12 is made up of following: shell 313; Can be by the chuck in shell 313 316 of chilled water; By being positioned in the shell 313 and being connected to the rotor 314 that the rotary body of centre rotational axis 312 is formed, described rotor high-speed rotation and surface with the plurality of grooves of being provided with; Be arranged at rotor 314 peripheries and keep the stator 310 of certain intervals between self and the rotor simultaneously, described stator has the surface of the plurality of grooves of being provided with; Be used to introduce the raw material input port 311 of raw material to be processed; Be used to handle the raw material escape hole 302 that powder is discharged in the back.Compartment between rotor 314 and the stator 310 is for pulverizing the district.

In the mechanical type comminutor that constitutes as mentioned above, after the powder stock with scheduled volume inputs to the raw material input port 311 of mechanical type comminutor from quantitative feeder shown in Figure 12 315, particle is introduced into the pulverization process chamber, and pulverizes when as follows: in the rotation of pulverization process chamber high speed and have the impact of generation between the stator 310 on rotor 314 and surface on surface of the plurality of grooves of being provided with the plurality of grooves of being provided with; Occur in a large amount of vortex flow very at a high speed after the impact; And high-frequency pressure vibration by flowing and producing.Afterwards, gains are discharged by raw material escape hole 302.The air of conveying toner-particle is expelled to the outside of device system via the pulverization process chamber by raw material escape hole 302, pipe 219, collection cyclone separator 229, bag hose 222 and suction drum blower fan 224.The present invention is preferred, and this is because following reason: comminuted powder raw material, so the pulverization process that can easily expect as mentioned above, and the amount of fine powder or meal is without any increase.In addition, the mechanical type comminutor that is used for pulverising step can be used for the surface modification step.It should be noted that in Figure 12 Reference numeral 212 expression spool cases (scroll casing); 220, divider; 240, the raw material hopper; 317, the chilled water supply port; 318, cooling water outlet; With 319, the cold air generation device.

In addition, Figure 13 illustrates along the section of outline view of D-D ' face intercepting shown in Figure 12.

The example of this mechanical type comminutor comprises: by the Kryptron as comminutor of Kawasaki Heavy Industries manufacturing; By Turbo Kogyo Co., the Turbo mill that Ltd. makes; Inomizer by Hosokawa Micron Corporation manufacturing; With the Super rotor that makes by Nisshin Engineering Inc..

In addition, will have the surface modification equipment system that can carry out the surface modification equipment of classification and surface modification treatment simultaneously shown in Figure 14 is preferred among the present invention.

Batch-type surface modification equipment shown in Figure 14 comprises: cylindrical body shell 30; Be installed on main body cover top so that can open the top board 43 that maybe can close; Has the fine powder discharge portion 44 that fine powder is discharged shell and fine powder vent pipe; The cooling jacket 31 that chilled water or freeze-point depressant pass through; As the dispersion rotor 32 of surface modification device, dispersion rotor 32 is present in the main body cover 30 and is connected on the centre rotational axis of shell; Dispersion rotor 32 has a plurality of square plates 33 on the surface thereon, and dispersion rotor 32 is the disc-like rotor along the predetermined direction high speed rotating; Be fixedly arranged at the liner that has predetermined space therebetween 34 of the periphery of dispersion rotor 32, liner 34 is provided with many grooves with dispersion rotor 32 facing surfaces; Be used for removing continuously at product in small, broken bits and have the fine powder of the predetermined particle diameter of being equal to or less than and the classification rotor 35 of superfine powder separately; Be used for cold air is introduced into the cold air intake 46 of main body cover 30; The side that is formed at main body cover 30 is used to introduce product in small, broken bits (raw material) and has raw material input port 37 and the input pipe of raw material supplying mouth 39; Have product escape hole 40 and product and extract mouth 42, be used for toner-particle after surface modification treatment is expelled to the product vent pipe of main body cover 30 outsides; But be installed between raw material input port 37 and the raw material supplying mouth 39 raw material supplying valve 38 with the switch of freely adjusting surperficial modification time; And be installed on product escape hole 40 and product and extract product exhaust valve 41 between mouthfuls 42.

The surface of liner 34 preferably has groove so that the modification effectively of the surface of toner-particle.Consider spin balancing, the quantity of square plate 33 is preferably even number.The classification rotor 35 preferred edges direction identical with the sense of rotation of dispersion rotor 32 rotated so that can improve classification efficiency, and the efficient that can improve the toner-particle surface modification.The fine powder vent pipe has fine powder escape hole 45, and described fine powder escape hole 45 is used for the outside that the fine powder that will remove by classification rotor 35 and superfine powder are expelled to equipment.

In main body cover 30, surface modification equipment has cylindric guide ring 36 as the guide piece that has perpendicular to the axle of top board 43.Guide ring 36 so is provided with so that its upper end by preset distance away from top board.Guide ring 36 is fixed on the main body cover 30 by supporting mass so that covers to small part classification rotor 35.The guide ring lower end so is provided with consequently by preset distance each square plate 33 away from dispersion rotor 32.

In surface modification equipment, the space between classification rotor 35 and the dispersion rotor 32 is divided into two spaces by guide ring 36: first space 47 of guide ring 36 outsides and second space 48 of guide ring 36 inside.First space 47 is for being used for product in small, broken bits and the particle that carries out surface modification treatment are introduced into the space of classification rotor 35.Second space is the space that is used for product in small, broken bits and the particle that carries out surface modification treatment are introduced into dispersion rotor.The gap portion and the liner 34 that are installed between each a plurality of square plate 33 on the dispersion rotor 32 constitute surface modified area 49.The periphery of classification rotor 35 and classification rotor 35 constitutes graded region 50.

The product in small, broken bits that is introduced into raw material hopper 380 via weight feed device 315, is passed through from the raw material input port 37 of input pipe, arrive raw material supplying valve 38, to be supplied to device interior from raw material supplying mouth 39.In surface modification equipment, the cold air that produces in cold air generation device 319 is supplied to the inside of main body cover from cold air input port 46, in addition, in the future the Cold water supply of self cooling water generates device 320 to cooling jacket 31 in case adjustment that will be in main body cover to predetermined temperature.The product of supplying with in small, broken bits arrives near the graded region 50 classification rotor 35, rotation in first space 47 of cylindric guide ring 36 outsides simultaneously, this be owing to: by fan blower 364 amount of air drawn; The eddy current that forms with the rotation of rotation by dispersion rotor 32 and classification rotor 35 carries out classification to be handled.Each the sense of rotation of orientation and dispersion rotor 32 and classification rotor 35 of eddy current that is formed at main body cover 30 is identical.

The fine powder that to remove by classification rotor 35 and the superfine powder inhalation power by fan blower 364 sucks from the slit of classification rotor 35, and collects by cyclone separator 369 and bag 362 via the fine powder escape hole 45 and the cyclone inlet 359 of fine powder vent pipe.The product in small, broken bits of having removed fine powder and superfine powder arrives near the surface modified area 49 dispersion rotor 32 so that the liner 34 that square plate 33 (hammers) that particle possesses with dispersion rotor 32 and main body cover 30 possess carries out surface treatment via second space 48.Near the while that surface modified granules reaches classification rotor 35 once more is along guide ring 36 rotations, and fine powder and superfine powder are removed from the particle of surface modification by 35 classifications with the classification rotor.After handling the schedule time, open exhaust valve 41, from surface modification equipment, take out removing the fine powder of the particle diameter that has the predetermined particle diameter of being equal to or less than separately and the surface modification toner-particle of superfine powder.

To have and be adjusted to weight average particle diameter and the size distribution that predetermined weight average particle diameter and predetermined particle diameter distribute, and respectively control oneself and carry out surface modification and be transferred to the step of externally adding external additive by the device 321 that is used to transmit toner-particle with toner-particle with predetermined circularity.

Can be used in surface modification equipment of the present invention and have dispersion rotor 32, be used for the supply port 39, classification rotor 35 of product in small, broken bits (raw material) and from the fine powder escape hole of its vertical direction downside.Therefore, under normal conditions, the part that will be used to drive classification rotor 35 (as motor) additionally is arranged on classification rotor top, and the part that will be used to drive dispersion rotor 32 additionally is arranged on dispersion rotor 32 belows.For being used for surface modification equipment of the present invention, the vertical direction that is difficult to classification rotor 35 is supplied with product in small, broken bits (raw material), unlike for example the TSP grader that only has classification rotor 35 described in the JP2001-259451A (being made by Hosokawa Micron Corporation).

In the present invention, the position with maximum gauge of classification rotor 35 preferably has 30 to 120m/sec most advanced and sophisticated peripheral speed (tip circumferential speed).The classification rotor has more preferably 50 to 115m/sec, or more preferably 70 to 110m/sec most advanced and sophisticated peripheral speed also.The most advanced and sophisticated peripheral speed that is lower than 30m/sec is not preferred, and this is because classification output is easy to reduce, and the amount of the superfine powder in toner-particle is tending towards increasing.The most advanced and sophisticated peripheral speed that surpasses 120m/sec is easy to cause following problem: vibration equipment increases.

In addition, the position with maximum gauge of dispersion rotor 32 preferably has 20 to 150m/sec most advanced and sophisticated peripheral speed.Dispersion rotor 32 has more preferably 40 to 140m/sec, or more preferably 50 to 130m/sec most advanced and sophisticated peripheral speed also.The most advanced and sophisticated peripheral speed that is lower than 20m/sec is not preferred, and this is to be difficult to obtain to have separately the surface modified granules of enough circularities because become.The most advanced and sophisticated peripheral speed that surpasses 150m/sec is not preferred, and this is because cause particle to be easy on the equipment of adhering to owing to temperature in the equipment raises, and is easy to take place the reduction of toner-particle classification productive rate.The most advanced and sophisticated peripheral speed of each can be improved the productive rate of toner-particle classification when falling in the above-mentioned scope in setting classification rotor 35 and dispersion rotor 32, and the surface of each particle of modification effectively.It should be noted that in Figure 14 Reference numeral T1 represents to be used to measure the thermometer of cold air temperature; T2 is used to measure the thermometer of classification rotor rear temperature; M, motor.

Next, the image forming method that can be applicable to toner of the present invention will be described in detail.

(image forming method)

Fig. 8 to 10 shows the example of the image forming apparatus that adopts image forming method of the present invention separately.In Fig. 8, as the electrophotographic photosensitive element 1 (hereinafter can be called " Electrifier frame, photoreceptor ") of electrostatic latent image bearing carrier along arrow indicated direction rotation among the figure.Electrifier frame, photoreceptor 1 is charged by the charging equipment 2 as charging device.On the powered surfaces of Electrifier frame, photoreceptor 1, laser light L forms electrostatic latent image thus from form exposure sources 3 incidents of device as electrostatic latent image.Afterwards, electrostatic latent image is manifested as toner image by the developing apparatus 4 as developing apparatus, and be transferred on the transfer materials P by transfer apparatus 5 as transfer device.Transfer materials P is carried out photographic fixing to export as image by the fixation facility 6 as fixing device under heating.Can will remain on the Electrifier frame, photoreceptor surface and not the cleaning equipment 7 as cleaning device of the transfer printing residual toner by the transfer device transfer printing by as shown in Figure 9 reclaim.As selection, allow following steps: static polarity is offered the transfer printing residual toner, the pilot bruss charging equipment 8 as smoothing apparatus by as shown in figure 10 applies bias voltage simultaneously, and toner is formed device through above-mentioned charging device and electrostatic latent image is used for once more developing or reclaiming by developing apparatus.It should be noted that in Fig. 8 to 10 Reference numeral 2a represents the electric conductivity supporting mass; 2e, pressing spring (press spring); 4a, developer reservoir; 4b, developer carrier; 4c, the magnetic roller; 4d, the developer adjustment means; 4e, developer; 4f, the developer agitating member; 4g, the developer hopper; A, charging part; B, exposure portion; C, development section; D, transfer printing portion; S1, S2, S3 and S4, power supply.

Each step of the image forming method that adopts among the present invention will be described in greater detail in herein.

(charge step)

Charge step does not limit especially, as long as be used for by applying the device that electric charge to Electrifier frame, photoreceptor surface makes the electrophotographic photosensitive element charging.Can will be used to make the electrophotographic photosensitive element charging to resemble the equipment that charger contact with electrophotographic photosensitive element simultaneously, or be used for being used as charging device by the equipment that conductive rollers or scraper plate is contacted with electrophotographic photosensitive element electrophotographic photosensitive element is charged.

(electrostatic latent image formation step)

Can be with known exposure sources as the exposure device in the electrostatic latent image formation step.For example, semiconductor laser or light emitting diode are used as light source, and can use the scanning optical unit of forming by polygonal mirror, lens and mirror.

The zone that can form electrostatic latent image is divided into along the zone of main scanning direction and the zone of time direction of scanning, edge.In the zone of Electrifier frame, photoreceptor upper edge main scanning direction is along the turning axle direction that is parallel to Electrifier frame, photoreceptor, and scope is from beginning the zone with position to the position of finishing the usefulness laser beam irradiation of laser beam irradiation.In addition, be in view data in the zone of time direction of scanning, upper edge, Electrifier frame, photoreceptor surface corresponding to one page, scope is from the zone of position to the position of the final main scanning line of the enough laser beam irradiations of energy of enough laser beam irradiation first main scanning lines of energy.In this zone, with the laser beam irradiation polygonal rotating mirror that is derived from as the semiconductor laser of light source.Then, regular deflection is assembled with scanning lens with the laser light reflected bundle, and the exposure of the electrostatic latent image on Electrifier frame, photoreceptor is carried out thus along perpendicular to the focused beam acts multiple scanning of the main scanning direction of inferior direction of scanning in the top of the Electrifier frame, photoreceptor that will rotate along inferior direction of scanning.

Manifest with developer as toner image in development step forming the electrostatic latent image that is formed on the Electrifier frame, photoreceptor in the step at electrostatic latent image as mentioned above.

(development step)

The method that can be used in development step mainly can be categorized as and get rid of carrier single component contact developing method that needs and the bi-component developing method that comprises use toner and carrier.In the present invention, the viewpoint of the high image quality of the needs from conduct from boundless duplicating will provide description as an example by adopting the bi-component developing method.

The bi-component developing method is to comprise following method: go up the magnetic brush that forms the two-component developing agent with nonmagnetic toner and magnetic carrier at the developer carrier that itself has magnet (development sleeve); Be coated with carrier with the developer layer thickness adjustment means with magnetic brush layer with predetermined thickness; Transmit gains to the developing regional relative with Electrifier frame, photoreceptor; And, in developing regional, between Electrifier frame, photoreceptor and development sleeve, apply predetermined development bias voltage simultaneously by making magnetic brush approach the surface of Electrifier frame, photoreceptor or contacting with the surface of Electrifier frame, photoreceptor, above-mentioned electrostatic latent image is manifested as toner image.

The example that can be used in the magnetic carrier in this two-component developing agent comprises iron powder carrier, ferrite carrier and by the magnetic fine grained being scattered in the resin carrier that the magnetic fine grained that obtains in the resin glue disperses.Because the ratio resistance of iron powder carrier itself is low, so the electric charge of electrostatic latent image leaks so that upset electrostatic latent image by carrier.As a result, image deflects appear sometimes.In addition, ferrite carrier itself has high relatively ratio resistance, but because the big saturation magnetization of this carrier causes magnetic brush to be tending towards rigidity, the brush mark that therefore occurs magnetic brush sometimes on toner image is inhomogeneous.So preferably have true specific gravity 2.5g/cm ³To 5.2g/cm ³Magnetic carrier.For example, be fit to use by the magnetic fine grained being scattered in the resin carrier of the magnetic fine grained dispersion that obtains in the resin glue.The resin carrier that the magnetic fine grained disperses is compared with ferrite carrier has high ratio resistance, and have little saturation magnetization and a little true specific gravity, therefore the resin carrier that disperses of magnetic fine grained prevents that the electric charge of electrostatic latent image from leaking, and not make magnetic brush be rigidity.Therefore, the resin carrier that preferred magnetic fine grained disperses, this is neither to have the good toner image that image deflects do not have the brush mark unevenness yet because can form.

In addition, the resin carrier of magnetic fine grained dispersion can have resinous coat on its surface.Constitute resin-coated material and only must comprise resin glue at least; Described layer can comprise adjuvant as the electric conductivity fine grained of resistance adjustment agent, be used to form the fine grained of irregularity degree or have the charge control agent that electric charge is applied to the character of toner.In addition, can use for example processing of coupling agent, so that improve the surface of carrier and the cohesive between the resinous coat.

(transfer step)

The method that can adopt in transfer step is following method: comprise transfer printing the lip-deep toner image of Electrifier frame, photoreceptor to the transfer materials simultaneously transfer member resemble the method that does not contact the corona transfer member with Electrifier frame, photoreceptor, contact with Electrifier frame, photoreceptor with transfer printing in the method for the lip-deep toner image of Electrifier frame, photoreceptor to the transfer materials with comprising making transfer member such as roller or not having sideband.

(cleaning)

In addition, image forming method of the present invention can further comprise: after transfer printing and the time point before the charge step, with the cleaning of as shown in Figure 9 the transfer printing residual toner of cleaning equipment 7 cleaning on Electrifier frame, photoreceptor.The example that can be used in the method for cleaning comprises known method such as scraper plate cleaning, brush cleaning and roller cleaning.

(level and smooth step)

In addition, purpose for the charged polarity homogenising that makes the transfer printing residual toner on the Electrifier frame, photoreceptor, image forming method of the present invention can further comprise the level and smooth step that relates to the use smoothing apparatus with bias voltage applying device 8 as shown in figure 10, so that after transfer printing and the level and smooth transfer printing residual toner of time point before the charge step, and can increase the recovery of transfer printing residual toner when developing.

In level and smooth step, preferred negative charging property toner, this is can alleviate the adhesion of transfer printing residual toner to charging member because in charge step negative charging transfer printing residual toner is applied bias voltage.In the case, increased the recovery of transfer printing residual toner when developing.In addition, the preferred level and smooth member of brush shape that uses.In addition, preferably provide the level and smooth member of a plurality of this type as mentioned above, this is because can alleviate the adhesion of transfer printing residual toner to charging member, and increases the recovery of transfer printing residual toner when developing.

(photographic fixing step)

Fixation facility is as the hard roller class fixation facility of tradition be made up of pair of rolls and any can be used in the photographic fixing step in this band fixation facility as shown in Figure 2, and described band fixation facility uses the speed that meets recently image forming apparatus to increase and the light compression set shadow system of the demand of energy consumption reduction.In the present invention, from the speed increase and the energy consumption reduction of image forming apparatus, and the acquired viewpoint of recording materials variation, will provide description as an example by adopting the band photographic fixing.

Photographic fixing has little thermal capacity because light compression set shadow system is as band, reaches the time that photographic fixing design temperature (adjusting temperature) needs so this system can shorten system temperature, and quick startability excellence.In addition, this system has the following advantages: fixation unit itself can reduce size and weight, and this is because system does not resemble the hard roller system of tradition, does not use thick metal parts or a plurality of well heater.

In addition, in the band photographic fixing, at least a member that forms roll gap is no sideband, therefore can easily form wide fusing nip width (wide roll gap).As a result, can prolong the time that adds thermal recording material, therefore for the high speed photographic fixing, the band photographic fixing is favourable.In addition, aspect high gloss and high chroma, the band photographic fixing is favourable.On the contrary, in the hard roller system of tradition, form the thickness that wide roll gap need increase elastic layer, so thermal capacity increases.Therefore, aspect energy-conservation, this system is disadvantageous.Therefore, in the present invention, preferred use can easily form wide roll gap and the band photographic fixing that do not increase elastic layer thickness as have little thermal capacity and the speed that can reach increase and energy-conservation between the photographic fixing system of compatibility.

On the other hand, in above-mentioned band photographic fixing, can form wide roll gap,, and be easy to inhomogeneous in the fixing temperature distribution of roll gap portion still because continuous the duplicating causes being easy to take place the fixing temperature reduction.In addition, the photographic fixing pressure distribution in roll gap portion also is easy to inhomogeneous.Applied pressure increases and to cause that band is being used for sliding on the rotary body of rotating band in the band photographic fixing, or causes that band moves to a left side or the right side of roller of suspension strap between it, so applied pressure must reduce.As mentioned above, " applied pressure " is tending towards light with comparing under the situation of hard roller system in band.

Yet, use toner of the present invention can solve the problem of the above-mentioned care of this light compression set shadow system, described light compression set shadow system can satisfy in the mode of excellence recently to pushing the speed and energy-conservation demand.

(full-colour image forming device)

In addition, Figure 11 illustrates the example of the full-colour image forming device that adopts image forming method of the present invention.The image forming apparatus that is shown in Figure 11 is for having the four station laser beam printers at four images formation stations (station).Form the station corresponding to four kinds of color settings image separately: pinkish red (M) look, green grass or young crops (C) look, Huang (Y) look and black (K) look.Each image forms station (P _K, P _Y, P _CAnd P _M) be to be used to develop have the device of the image of each color with transfer printing.The image that is used for black toner forms station P _K, the image that is used for Yellow toner forms station P _Y, the image that is used for cyan toner forms station P _CForm station P with the image that is used for magenta toner _MPut in order and be not limited to the order shown in the figure, and the sense of rotation of each electrophotographic photosensitive element and roller also is not limited among the figure by the arrow indicated direction.In Figure 11, as electrophotographic photosensitive element 1K, 1Y, 1C and the 1M of electrostatic latent image bearing carrier respectively along rotating by the arrow indicated direction among the figure.Each Electrifier frame, photoreceptor passes through the corresponding apparatus charging as charging equipment 2K, 2Y, 2C and the 2M of charging device.Laser light L forms electrostatic latent image thus for being incident on the charging surface of each Electrifier frame, photoreceptor from the relevant device that forms exposure sources 3K, 3Y, 3C and the 3M of device as electrostatic latent image.Afterwards, electrostatic latent image is manifested by developing apparatus 10K, 10Y, 10C and 10M as developing apparatus as toner image, and be transferred on the transfer materials P, thereby and make transfer materials P under heating, carry out photographic fixing to export as image by fixation facility 12 as fixing device by transfer apparatus 19K, 19Y, 19C and 19M as transfer device.Herein, Reference numeral 17K, 17Y, 17C and 17M represent developer carrier separately, travelling belt 13 are set to hang between driven roller 14 and driven voller 15.By driving along the rotation of arrow a indicated direction along the rotation of the driven roller 14 of arrow b direction indication, and the transfer materials P that carrying is supplied with by paper supply unit 11 forms station P to transmit transfer materials to image continuously with travelling belt 13 _M, P _C, P _YAnd P _K

Hereinafter, will describe in detail about measuring method of the present invention.

(measuring the THF insoluble substance of resin glue in toner by the soxhlet extraction of toner)

Weighing 1.0g toner (W1 (g)).The toner of weighing is positioned in the extraction thimble (No.86R (size 28 * 100mm) for example, make by ADVANTEC), and with its soxhlet's extractor of packing into, so that by using 200ml tetrahydrofuran (THF) toner to be extracted 2,4,8 and 16 hours as solvent.In the case, be to extract under this reflux rate once in every about 4 to 5 minutes in the extraction cycle of solvent.After extraction is finished, with the extraction thimble taking-up and 40 ℃ of following vacuum drying 8 hours, the amount (W2 (g)) of weighing extraction residue.

Next, be determined at the weight (W3 (g)) of the burning ash in the toner.Measure the weight of burning ash by following steps.Be positioned over about 2g sample in the magnetic crucible that 30-ml accurately weighed in advance and accurately weigh so that the accurate quality (Wa (g)) of weighing sample.Crucible is positioned in the electric furnace, heated about 3 hours down, in electric furnace, leave standstill cooling, before accurate weighing crucible quality, in exsiccator, leave standstill cooling at normal temperatures more than 1 hour at about 900 ℃.Measure the weight (Wb (g)) of burning ash from following equation:

(Wb/Wa) * 100=burns ash content (quality %).

Can determine the quality (W3 (g)) of the burning ash of sample from burning ash content.

W3=W1 * [burning ash content (quality %)] (g)

Can determine the THF insoluble substance from following equation:

THF insoluble substance={ (W2-W3)/(W1-W3) } * 100 (%).

Should note, by the weight (W2 (g)) of the extraction residue that uses the scheduled volume of weighing resin (W1 (g)) and determine by identical as mentioned above step, measure the THF insoluble substance of the sample that does not contain the component except that resin such as resin glue from following equation:

THF insoluble substance=(W2/W1) * 100 (quality %).

(measuring the molecular weight distribution of resin glue)

Measure chromatogram molecular weight under the following conditions by gel permeation chromatography (GPC).In this application, HLC-8120GPC (being made by TOSOH CORPORATION) is used for measuring.Post is stable in the hot cell under 40 ℃.Tetrahydrofuran (THF) flow velocity with 1ml/min under this temperature as solvent is flowed in this post, and the THF sample solution that about 50 to 200 μ l have a resin glue that is adjusted to 0.05 to 0.6 quality % sample concentration injected be used for measuring.In the molecular weight of measuring samples, from the molecular weight distribution that calculation sample has that concerns between the logarithm value of the analytic curve made by several monodisperse polystyrene standard models and the counting (retention time).The example that is used to prepare the polystyrene standard sample of the analytic curve that can use comprises having 6 * 10 separately ², 2.1 * 10 ³, 4 * 10 ³, 1.75 * 10 ⁴, 5.1 * 10 ⁴, 1.1 * 10 ⁵, 3.9 * 10 ⁵, 8.6 * 10 ⁵, 2 * 10 ⁶Or 4.48 * 10 ⁶The sample by TOSOH CORPORATION or Pressure Chemical Co. manufacturing of molecular weight.Suitably use at least about ten polystyrene standard samples.Differential refraction (RI) detecting device is used as detecting device.Recommend combination with the many Aquapak A-440 posts that are obtained commercially with acting on accurate measurement 10 ³To 2 * 10 ⁶The post of molecular weight region.The example of combination comprises the shodex GPC KF-801 that is made by S howa Denko K.K., 802,803,804,805,806 and 807 combination; μ-styragel 500,10 by Waters Corporation manufacturing ³, 10 ⁴With 10 ⁵Combination.

(measuring temperature (Tfb) that resin glue begins to flow out and the softening point (1/2 method temperature (T1/2)) of resin glue) with flow tester

Measure based on JIS K 7210 usefulness overhead system flow testers (elevated type flowtester).Concrete measuring method below is shown.

When will be by make sample that about 1.1g resin granulation obtains when using overhead system flow tester (making) with molding press with the heating rate heating of 6 ℃/min by Shimadzu Corporation; the load of 20kgf (196N) is put on sample by using plunger, extrude so that will have the nozzle of 1mm diameter and 1mm length.Based on the result who extrudes, the plunger amount of falling of drawing (slamp value)-temperature curve.By Tfb (℃) the expression sample temperature that begins to flow out.The height of sigmoid curve (total discharge) represented by h, will be defined as corresponding to the temperature (temperature when resin flows out half) of h/2 resin 1/2 method temperature (T1/2) (℃).In the present invention, 1/2 method temperature is defined as resin softening point (Tm) (℃).

(measure the glass transition temperature (Tg) (℃) and the highest endothermic peak of toner) of resin glue

The highest endothermic peak of glass transition temperature of resin glue (Tg) and toner can be measured by using differential scanning calorimeter (dsc measurement equipment) or DSC 2920 (being made by TA Instruments Japan Inc.) according to ASTM D 3418-82.

Temperature curve: intensification I (20 ℃ to 200 ℃, 10 ℃ of heating rates/min)

Cooling I (200 ℃ to 20 ℃, 10 ℃ of rate of temperature fall/min)

Intensification II (20 ℃ to 200 ℃, 10 ℃ of heating rates/min)

Measuring method is as described below.The measuring samples of accurately weighing 5 to 20mg, preferred 10mg.Sample is packed in the aluminium dish.Empty aluminium dish is used as reference.At normal temperature and normal down wet, in 30 to 200 ℃ measurement temperature range, measure with the heating rate of 10 ℃/min.To in the process of intensification II, be defined as the Tg of resin glue corresponding to the temperature of mid point from baseline to displacement region.In addition, the highest endothermic peak of toner is: in the process of intensification II, in the zone that is equal to or higher than the endothermic peak of resin glue (Tg), have from the peak of the maximum height of baseline.Overlapping so that when being difficult to judge the highest endothermic peak, the peak that will have maximum height in overlap peak outside the local maximum peak is defined as the highest endothermic peak of toner of the present invention when the endothermic peak (Tg) of resin glue and another endothermic peak.

(measuring the storage elastic modulus of toner)

Measure storage elastic modulus G ' (140 ℃) of the toner among the present invention by the following method.

ARES (being made by Rheometric Scientific F.E.Ltd.) is used as measuring equipment.In 60 to 200 ℃ temperature range, measure to store under the following conditions elastic modulus G '.

Measured material (jig): use round parallel-plate with 8mm diameter.At the tazza of detent side use corresponding to the circle parallel-plate.The bottom surface and the gap between the plectane of tazza are about 2mm.

Measuring samples: before using, be disk samples at the pressurization compacted under with the about 8mm of diameter and highly about 2mm with toner.

Survey frequency: 6.28rad/sec

Measure the setting of distortion: initial value is set at 0.1%, measures according to automatic measurement pattern then.

The correction of the elongation of sample: regulate according to automatic measurement pattern.

Measure temperature: under the speed of 2 ℃/min, be warming up to 200 ℃ from 60 ℃.

Will by said method in 60 to 200 ℃ temperature range, measure store the storage elastic modulus G of elastic modulus G ' time under 140 ℃ ' value defined be G ' (140 ℃).

(measuring the size distribution of toner)

Coulter Counter TA-II or Coulter Multisizer II (by BeckmanCoulter, Inc makes) are used as measuring equipment.The NaCl aqueous solution that will have about 1% concentration is as electrolyte solution.Can will be used as electrolyte solution by the electrolyte solution that uses a grade sodium chloride or for example ISOTON (registered trademark)-II (by Coulter Scientific Japan, Co. makes) preparation.

Measuring method is as described below.To be added into 100 to 150ml electrolyte aqueous solutions as 0.1 to the 5ml surfactant (preferred alkyl benzene sulfonate) of spreading agent.In addition, 2 to 20mg measuring samples are added in the potpourri.The electrolyte solution of suspended sample was carried out dispersion treatment about 1 to 3 minute with ultrasonic dispersal unit.For each passage, the volume of sample particle and quantity are measured by means of the 100-μ m aperture as the aperture by using measuring equipment, and the volume distributed median of calculation sample and distributed number.From distributing, these gained determine the weight average particle diameter (D4) of sample.Will with passage comprise 13 passages: the passage with particle size range 2.00 to 2.52 μ m, 2.52 to 3.17 μ m, 3.17 to 4.00 μ m, 4.00 to 5.04 μ m, 5.04 to 6.35 μ m, 6.35 to 8.00 μ m, 8.00 to 10.08 μ m, 10.08 to 12.70 μ m, 12.70 to 16.00 μ m, 16.00 to 20.20 μ m, 20.20 to 25.40 μ m, 25.40 to 32.00 μ m and 32 to 40.30 μ m.

(measuring the average circularity of toner)

The average circularity of toner with streaming particle image analyser " FPIA-3000 type " (making) by Sysmex Corporation when the calibration operation measurement and analysis condition under measure.

The measuring principle of streaming particle image analyser " FPIA-3000 type " is as follows: flow particles taken a picture as rest image, and analysis image.The sample that is added into the sample chamber is fed to flat sheath stream chamber (flat sheath flowce1l) with sample inhalation syringe.The sample that is fed to flat sheath stream chamber is sandwiched between the sheath fluid to form mild stream.To shine with 1/60 second interval with stroboscope light through the sample of smooth epitheca flow chamber inside, flow particles can be taken a picture as rest image thus.In addition, with the clear photograph of particle, this is because the mobile of particle is mild.With the CCD camera particle image is taken a picture, and make the image of shooting under the Flame Image Process resolution of 512 * 512 (every pixel 0.37 * 0.37 μ m), carry out Flame Image Process, so that the edge of each particle image of taking a sample.Then, measure the projected area, girth etc. of each particle image.

Next, measure the projected area S and the perimeter L of each particle image.Equivalent circle diameter and circularity are determined by using above-mentioned area S and perimeter L.Term " equivalent circle diameter " is meant to have and the projected area of particle image diameter of a circle of the same area." circularity " is defined as value by obtaining divided by the girth of particle projection image from the girth of the circle determined by equivalent circle diameter, and calculates from following formula:

C＝2×√(π×S)/L。

When particle image was circle, the circularity of the particle in the image became 1.When the degree of irregularity in the particle image periphery increased, circularity showed the value that reduces.

Calculate after the circularity of each particle, will be divided into 800 parts in the circularity in 0.200 to 1.000 scope, the average circularity of particle is calculated by the quantity of using the particle of measuring.

The measurement and the analysis condition of streaming particle image analyser " FPIA-3000 type " when in addition, following table shows calibration operation.

Table 1

The concrete measuring method of the present invention is as described below.With 0.1 to 5ml surfactant as spreading agent, preferred neopelex is added into after the 20ml ion exchange water, the 20mg measuring samples is added in the potpourri, and whole materials were carried out dispersion treatment 2 minutes with desktop ultrasonic cleaning with the output of 50kHz oscillation frequency and 150W electricity and dispersion machine (as ＂ VS-150 ＂ (being made by VELVO-CLEAR)), obtain the dispersion liquid that is used to measure thus.In the case, dispersion liquid is suitably cooled off to have more than 10 ℃ to the temperature below 40 ℃.

The streaming particle image analyser that standard object lens (under 10 enlargement ratios) will be installed is used for measuring, and particle sheath " PSE-900A " (being made by SYSMEX CORPORATION) is used as sheath fluid.To introduce in the streaming particle image analyser according to the dispersion liquid of above-mentioned steps preparation, measure 3,000 toner-particles according to HPF measurement pattern and tale pattern.Binary-state threshold when grain size analysis be set at 85% and the particle diameter that will analyze be defined in separately corresponding to equivalent circle diameter be more than the 2.00 μ m to the situation of the particle diameter below the 200.00 μ m, determine the average circularity of toner.

Before beginning to measure, carry out automatic focus by using standard latex particle (by for example obtaining) by the 5200A that Duke Scientific makes with the ion exchange water dilution.Afterwards, preferably focused in per two hours from beginning to measure.

Should note, in each example of the application, use the streaming particle image analyser of the calibration certificate that has carried out calibration operation by SYSMEXCORPORATION and accepted to issue by SYSMEXCORPORATION, and be defined as except the particle diameter that will analyze corresponding to equivalent circle diameter be separately more than the 2.00 μ m to the particle diameter below the 200.00 μ m, measure under identical measurement and the analysis condition when accepting calibration certificate.

(estimating the bin stability of toner)

Weighing 5.0g toner in cup (polycup).It respectively is the thermostat 7 days of 45 ℃ and 50 ℃ that cup (polycup) is placed.Carry out visual evaluation based on following standard.

A: comfortable 45 ℃ and 50 ℃ placement is before identical down for mobile basic and each of toner.

B: the flowability of toner is basic, and placement is before identical down with 45 ℃, but observes the aggregation of the following size of 2mm of the enough finger destruction of energy under 50 ℃.

C: under 45 ℃, observe the aggregation of the following size of 2mm, and under 50 ℃, observe the aggregation of the following size of 5mm, but this aggregation can not destroy with finger.

D: under each 45 ℃ and 50 ℃, all observe aggregation, and aggregation can not destroy with finger greater than the 5mm size.

E: under each 45 ℃ and 50 ℃, all observe aggregation, and aggregation can not destroy with finger greater than the 10mm size.

Embodiment

Hereinafter, will the present invention be described in more detail by concrete mode of producing example and embodiment.Yet the present invention never is limited to these embodiment.

(low softening point resin production example 1)

Will be as the dimer of the 5 mass parts styrene that are used for the vinyl-based copolymer material, 2.5 mass parts 2-EHAs, 1 mass parts fumaric acid and 2.5 mass parts α-Jia Jibenyixi and the dicumyl peroxide tap funnel of packing into.In addition, with 30 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 10 mass parts terephthalic acid (TPA)s, 5 mass parts trimellitic anhydrides, 24 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four neck flasks.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in sheathing formula (mantle) well heater.With after the nitrogen replacement four neck flask interior, the temperature of flask interior raises gradually and is stirred in potpourri in the flask simultaneously.When under 130 ℃ temperature, stirring the mixture, monomer, crosslinking chemical and the polymerization initiator of the vinyl-based copolymer that is shown in Table 2 splashed into the potpourri through about 4 hours from aforesaid tap funnel.Next, the temperature of flask interior is increased to 200 ℃, and potpourri was reacted 2 hours, obtains low softening point resin (L-1) thus.Table 2 illustrates the composition of gained low softening point resin, and table 4 illustrates the physical property of resin.

(low softening point resin production example 2)

Will be as the dimer of the 10 mass parts styrene that are used for vinyl-based material, 5 mass parts 2-EHAs, 2 mass parts fumaric acid and 5 mass parts α-Jia Jibenyixi and the dicumyl peroxide tap funnel of packing into.In addition, with 25 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 15 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 10 mass parts terephthalic acid (TPA)s, 5 mass parts trimellitic anhydrides, 23 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four neck flasks.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.With after the nitrogen replacement four neck flask interior, the temperature of flask interior raises gradually and is stirred in potpourri in the flask simultaneously.When under 130 ℃ temperature, stirring the mixture, monomer, crosslinking chemical and the polymerization initiator of the vinyl-based copolymer that is shown in Table 2 splashed into the potpourri through about 4 hours from aforesaid tap funnel.Next, the temperature of flask interior is increased to 200 ℃, and potpourri was reacted 2 hours, obtains low softening point resin (L-2) thus.Table 2 illustrates the composition of gained low softening point resin, and table 4 illustrates the physical property of resin.

(low softening point resin production example 3)

With 30 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts terephthalic acids, 3 mass parts trimellitic anhydrides, 27 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four-necked bottle.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.Under nitrogen atmosphere, the potpourri in the flask was reacted under 210 ℃ 2 hours, obtain vibrin thus.

Next, di-t-butyl peroxide is added in the potpourri of 83 mass parts polystyrene and 1 mass parts n-butyl acrylate, and with whole materials through in the dimethylbenzene that splashed into the heating of 200 mass parts in 4 hours.In addition, gains are carried out polyreaction 2 hours under refluxing xylene, and remove the temperature desolvate simultaneously under reduced pressure gains by distillation and be heated to 200 ℃, obtain the styrene-propene acid resin thus.

Above-mentioned vibrin and the 20 mass parts styrene-propene acid resin that obtains like this that 80 mass parts are so obtained mix with the Han Xieer mixer, obtain low softening point resin (L-3) thus.Table 2 illustrates the composition of gained low softening point resin, and table 4 illustrates the physical property of resin.

(low softening point resin production example 4 and 5)

Except will be in low softening point resin production example 3 mixing ratio between gained vibrin and the gained styrene-propene acid resin change into the mixing ratio shown in the table 2, obtain low softening point resin (L-4) and (L-5) separately in the mode identical with low softening point resin production example 3.Table 2 illustrates the composition of gained low softening point resin, and table 4 illustrates the physical property of resin.

(low softening point resin production example 6)

With 30 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts terephthalic acids, 3 mass parts trimellitic anhydrides, 27 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four-necked bottle.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.Under nitrogen atmosphere, the potpourri in the flask was reacted under 210 ℃ 1 hour, obtain low softening point resin (L-6) thus.Table 2 illustrates the composition of gained low softening point resin, and table 4 illustrates the physical property of resin.

(high softening point resin production example 1)

Will be as the dimer of the 10 mass parts styrene that are used for the vinyl-based copolymer material, 5 mass parts 2-EHAs, 2 mass parts fumaric acid and 5 mass parts α-Jia Jibenyixi and the dicumyl peroxide tap funnel of packing into.In addition, with 25 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 15 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 10 mass parts terephthalic acid (TPA)s, 5 mass parts trimellitic anhydrides, 23 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four neck flasks.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.With after the nitrogen replacement four neck flask interior, the temperature of flask interior raises gradually and is stirred in potpourri in the flask simultaneously.When under 130 ℃ temperature, stirring the mixture, monomer, crosslinking chemical and the polymerization initiator of the vinyl-based copolymer that is shown in Table 3 splashed into the potpourri through about 4 hours from aforesaid tap funnel.Next, the temperature of flask interior is increased to 200 ℃, and potpourri was reacted 5 hours, obtains high softening point resin (H-1) thus.Table 3 illustrates the composition of gained low softening point resin, and table 5 illustrates the physical property of resin.

(high softening point resin production example 2)

Will be as the dimer of the 10 mass parts styrene that are used for the vinyl-based copolymer material, 5 mass parts 2-EHAs, 2 mass parts fumaric acid and 5 mass parts α-Jia Jibenyixi and the dicumyl peroxide tap funnel of packing into.In addition, with 25 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 15 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 10 mass parts terephthalic acid (TPA)s, 5 mass parts trimellitic anhydrides, 5 mass parts hexane diacids, 18 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four neck flasks.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.With after the nitrogen replacement four neck flask interior, the temperature of flask interior raises gradually and is stirred in potpourri in the flask simultaneously.When under 130 ℃ temperature, stirring the mixture, monomer, crosslinking chemical and the polymerization initiator of the vinyl-based copolymer that is shown in Table 3 splashed into the potpourri through about 4 hours from aforesaid tap funnel.Next, the temperature of flask interior is increased to 200 ℃, and potpourri was reacted 5 hours, obtains high softening point resin (H-2) thus.Table 3 illustrates the composition of gained high softening point resin, and table 5 illustrates the physical property of resin.

(high softening point resin production example 3)

Will be as the dimer of the 15 mass parts styrene that are used for the vinyl-based copolymer material, 7.5 mass parts 2-EHAs, 3 mass parts fumaric acid and 7.5 mass parts α-Jia Jibenyixi and the dicumyl peroxide tap funnel of packing into.In addition, with 20 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 15 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 10 mass parts terephthalic acid (TPA)s, 5 mass parts trimellitic anhydrides, 5 mass parts hexane diacids, 12 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four neck flasks.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.With after the nitrogen replacement four neck flask interior, the temperature of flask interior raises gradually and is stirred in potpourri in the flask simultaneously.When under 130 ℃ temperature, stirring the mixture, monomer, crosslinking chemical and the polymerization initiator of the vinyl-based copolymer that is shown in Table 3 splashed into the potpourri through about 4 hours from aforesaid tap funnel.Next, the temperature of flask interior is increased to 200 ℃, and potpourri was reacted 5 hours, obtains high softening point resin (H-3) thus.Table 3 illustrates the composition of gained high softening point resin, and table 5 illustrates the physical property of resin.

(high softening point resin production example 4 and 5)

With 30 mass parts polyoxypropylenes (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts polyoxyethylene (2.2)-2, two (4-hydroxy phenyl) propane of 2-, 20 mass parts terephthalic acids, 3 mass parts trimellitic anhydrides, 27 mass parts fumaric acid and the dibutyltin oxide glass 4-that packs into rises in the four-necked bottle.Thermometer, stirring rod, condenser and nitrogen ingress pipe are mounted to four neck flasks, and four neck flasks are positioned in the sheathing formula well heater.Under nitrogen atmosphere, the potpourri in the flask was reacted under 210 ℃ 5 hours, obtain vibrin thus.

Next, di-t-butyl peroxide is added in the potpourri of 83 mass parts polystyrene and 1 mass parts n-butyl acrylate, and with whole materials through in the dimethylbenzene that splashed into the heating of 200 mass parts in 4 hours.In addition, gains are carried out polyreaction 5 hours under refluxing xylene, and remove the temperature desolvate simultaneously under reduced pressure gains by distillation and be heated to 200 ℃, obtain the styrene-propene acid resin thus.

The vibrin of above-mentioned acquisition like this and the styrene-propene acid resin that so obtains are mixed with the Han Xieer mixer, so that the ratio of components between vibrin and the styrene-propene acid resin is the ratio that is shown in table 3, obtain high softening point resin (H-4) and (H-5) thus.Table 3 illustrates the composition of gained low softening point resin, and table 5 illustrates the physical property of resin.

(middle softening point production of resins example 1)

Except will changing into 3 hours in the reaction time from 2 hours, softening point resin (M-1) in producing in the mode identical with low softening point resin production example 1.Table 6 illustrates the physical property of the middle softening point resin (M-1) that obtains herein.

(middle softening point production of resins example 2)

Except will changing into 3 hours in the reaction time from 2 hours, softening point resin (M-2) in producing in the mode identical with low softening point resin production example 2.Table 6 illustrates the physical property of the middle softening point resin (M-2) that obtains herein.

It should be noted that table 4 to 6 in, Mp is illustrated in the molecular weight of the main peak in the molecular weight distribution that its place is provided with the resin by gpc measurement, Tg represents the glass transition temperature of resin.

Table 2

The material of table 2. low softening point resin is formed tabulation

	The composition of polyester unit	The composition of vinyl class in polymer unit	The ratio of components of polyester unit and vinyl class in polymer unit (ratio of components)
				(L-1)	PO-BPA、EO-BPA TPA、FA、TMA	St, 2EHA α-Jia Jibenyixi	90/10
(L-2)	PO-BPA、EO-BPA TPA、FA、TMA	St, 2EHA α-Jia Jibenyixi	80/20
				(L-3)	PO-BPA、EO-BPA TPA、FA、TMA	St、BA	80/20
(L-4)	PO-BPA、EO-BPA TPA、FA、TMA	St、BA	85/15
				(L-5)	PO-BPA、EO-BPA TPA、FA、TMA	St、BA	50/50
(L-6)	PO-BPA、EO-BPA TPA、FA、TMA	Do not have	100/0

PO-BPA: the propylene oxide adduct FA of bisphenol-A: fumaric acid St: styrene

TPA: terephthalic acid (TPA) 2-EHA: acrylic acid

EO-BPA: the ethylene oxide adduct of bisphenol-A

The 2-ethylhexyl ester

TMA: trimellitic anhydride α-Jia Jibenyixi

Hexane diacid BA: butyl acrylate

Table 3

The material of table 3. high softening point resin is formed tabulation

	The composition of polyester unit	The composition of vinyl class in polymer unit	The ratio of components of polyester unit and vinyl class in polymer unit (ratio of components)
				(H-1)	PO-BPA、EO-BPA TPA、FA、TMA	St, 2EHA α-Jia Jibenyixi	80/20
(H-2)	PO-BPA, EO-BPA TPA, FA, TMA, hexane diacid	St, 2EHA α-Jia Jibenyixi	80/20
				(H-3)	PO-BPA, EO-BPA TPA, FA, TMA, hexane diacid	St, 2EHA α-Jia Jibenyixi	70/30
(H-4)	PO-BPA、EO-BPA TPA、FA、TMA	St、BA	80/20
				(H-5)	PO-BPA、EO-BPA TPA、FA、TMA	St、BA	60/40

PO-BPA: the epoxypropane adduction FA of bisphenol-A: fumaric acid St: styrene

Thing

EO-BPA: bisphenol-A epoxy ethane adduction 2-EHA: acrylic acid 2-ethyl is own

TPA: terephthalic acid (TPA)

The thing ester

TMA: trimellitic anhydride α-Jia Jibenyixi

Hexane diacid BA: butyl acrylate

Table 4

The physical property tabulation of table 4. low softening point resin

Table 5

The physical property tabulation of table 5. high softening point resin

Table 6

The physical property of softening point resin tabulation in the table 6.

(masterbatch production example 1)

Produce masterbatch (P-1) by using following material and following production method.

Middle softening point resin (M-1) 50 mass parts

C.I. pigment blue 15: 3 50 mass parts

With above-mentioned material Han Xieer mixer (FM-75 type, by Mitsui MiikeMachinery Co., Ltd. makes) mix, then biaxial extruder (the PCM-30 type with the temperature that is set to 120 ℃ is also used in the potpourri fusion, by Ikegai, Ltd. makes) mediate.Gained is mediated product cooling, and be the piece that has the following size of 1mm separately, obtain masterbatch (P-1) thus with the hammer-mill coarse crushing.

(masterbatch production example 2)

Produce masterbatch (P-2) by using following material and following production method.

Middle softening point resin (M-2) 50 mass parts

C.I. pigment blue 15: 3 50 mass parts

With above-mentioned material Han Xieer mixer (FM-75 type, by Mitsui MiikeMachinery Co., Ltd. makes) mix, then biaxial extruder (the PCM-30 type with the temperature that is set to 120 ℃ is also used in the potpourri fusion, by Ikegai, Ltd. makes) mediate.Gained is mediated product cooling, and be the piece that has the following size of 1mm separately, obtain masterbatch (P-2) thus with the hammer-mill coarse crushing.

Table 7

The tabulation of table 7. masterbatch

(toner production example 1)

Produce toner (T-1) by using following material and following production method.

Low softening point resin (L-1) 50 mass parts

High softening point resin (H-1) 50 mass parts

Masterbatch (P-1) 10 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (normal paraffin wax) (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.7 mass parts

With above-mentioned material Han Xieer mixer (FM-75 type, by Mitsui MiikeMachinery Co., Ltd. makes) mix, then biaxial extruder (the PCM-30 type with the temperature that is set to 120 ℃ is also used in the potpourri fusion, by Ikegai, Ltd. makes) mediate.Gained is mediated product cooling, and be the piece that has the following size of 1mm separately, obtain toner coarse crushing product thus with the hammer-mill coarse crushing.Gained toner coarse crushing product is in small, broken bits with this mechanical type comminutor as shown in figure 12.With toner coarse crushing product with being set to 120s ^-1The rotor rotation number pulverize.

Next, with gained product in small, broken bits with having the 100s of being set to ^-1The equipment of surface modification treatment as shown in figure 14 of dispersion rotor rotation number (corresponding to the rotation round speed of 130m/sec) carried out surface treatment 60 seconds, simultaneously with being set to 120s ^-1Classification rotor rotation number from product, remove fine grained.As a result, obtain toner-particle.

Then, 1.0 quality % had 100m ²The anatase-type titanium oxide of/g BET specific surface area and 1.0 quality % have 130m ²The hydrophobic silica of/g BET specific surface area is added in the 100 mass parts gained toner-particles, and with Han Xieer mixer (FM-75 type, by Mitsui Miike Machinery Co., Ltd. makes) at 30s ^-1Rotation number under with whole mixing of materials 10 minutes, obtain toner (T-1) thus.Table 8 illustrates the composition of the toner (T-1) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 2)

Produce toner (T-2) by using following material and following production method.

Low softening point resin (L-1) 70 mass parts

High softening point resin (H-2) 30 mass parts

Masterbatch (P-1) 10 mass parts

Ester type waxes (W-2: 7 mass parts 85 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.9 mass parts

Obtain toner (T-2) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (T-2) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 3)

Produce toner (T-3) by using following material and following production method.

Low softening point resin (L-2) 70 mass parts

High softening point resin (H-2) 30 mass parts

Masterbatch (P-2) 10 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-3: 7 mass parts 65 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

Obtain toner (T-3) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (T-3) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 4)

Produce toner (T-4) by using following material and following production method.

Low softening point resin (L-1) 90 mass parts

High softening point resin (H-1) 10 mass parts

Masterbatch (P-1) 10 mass parts

Husky rope wax (Sasol wax) (W-4: 7 mass parts 108 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.9 mass parts

Obtain toner (T-4) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (T-4) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 5)

Produce toner (T-5) by using following material and following production method.

Low softening point resin (L-2) 50 mass parts

High softening point resin (H-3) 50 mass parts

Masterbatch (P-2) 10 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-5: 7 mass parts 52 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

Obtain toner (T-5) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (T-5) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 6)

Produce toner (T-6) by using following material and following production method.

Low softening point resin (L-1) 90 mass parts

High softening point resin (H-1) 10 mass parts

Masterbatch (P-1) 10 mass parts

Husky rope wax (W-4: 7 mass parts 108 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 1.8 mass parts

Obtain toner (T-6) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (T-6) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 15 illustrates the chart 1 of toner.

(toner production example 7)

Produce toner (t-1) by using following material and following production method.

Low softening point resin (L-3) 30 mass parts

High softening point resin (H-4) 70 mass parts

C.I. pigment blue 15: 35 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

With above-mentioned material Han Xieer mixer (FM-75 type, by Mitsui MiikeMachinery Co., Ltd. makes) mix, then biaxial extruder (the PCM-30 type with the temperature that is set to 160 ℃ is also used in the potpourri fusion, by Ikegai, Ltd. makes) mediate.Gained is mediated product cooling, and be the piece that has the following size of 1mm separately, obtain toner coarse crushing product thus with the hammer-mill coarse crushing.Gained toner coarse crushing product is in small, broken bits with this mechanical type comminutor as shown in figure 12.With toner coarse crushing product with being set to 120s ^-1The rotor rotation number pulverize.

Next, with gained product in small, broken bits with having the 100s of being set to ^-1The equipment of surface modification treatment as shown in figure 14 of dispersion rotor rotation number (corresponding to the rotation round speed of 130m/sec) carried out surface treatment 60 seconds, simultaneously with being set to 120s ^-1Classification rotor rotation number from product, remove fine grained.As a result, obtain toner-particle.

Then, 1.0 quality % had 100m ²The anatase-type titanium oxide of/g BET specific surface area and 1.0 quality % have 130m ²The hydrophobic silica of/g BET specific surface area is added in the 100 mass parts gained toner-particles, and with Han Xieer mixer (FM-75 type, by Mitsui Miike Machinery Co., Ltd. makes) at 30s ^-1Rotation number under with whole mixing of materials 10 minutes, obtain toner (t-1) thus.Table 8 illustrates the composition of the toner (t-1) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(toner production example 8)

Produce toner (t-2) by using following material and following production method.

Low softening point resin (L-4) 100 mass parts

C.I. pigment blue 15: 35 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

With above-mentioned material Han Xieer mixer (FM-75 type, by Mitsui MiikeMachinery Co., Ltd. makes) mix, then biaxial extruder (the PCM-30 type with the temperature that is set to 160 ℃ is also used in the potpourri fusion, by Ikegai, Ltd. makes) mediate.Gained is mediated product cooling, and be the piece that has the following size of 1mm separately, obtain toner coarse crushing product thus with the hammer-mill coarse crushing.Gained toner coarse crushing product is in small, broken bits with this mechanical type comminutor as shown in figure 12.With toner coarse crushing product with being set to 120s ^-1The rotor rotation number pulverize.

Next, by using air flow type air classifier (Elbow jet is made by Matsubo Corporation) that gained product in small, broken bits is formed toner-particle.

Then, 1.0 quality % had 100m ²The hydrophobic silica that the anatase-type titanium oxide of/g BET specific surface area and 1.0 quality % have the 130m2/gBET specific surface area is added in the 100 mass parts gained toner-particles, and with Han Xieer mixer (FM-75 type, by Mitsui Miike Machinery Co., Ltd. make) under the rotation number of 30s-1 with whole mixing of materials 10 minutes, obtain toner (t-2) thus.Table 8 illustrates the composition of the toner (t-2) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(toner production example 9)

Produce toner (t-3) by using following material and following production method.

Low softening point resin (L-5) 30 mass parts

High softening point resin (H-5) 70 mass parts

C.I. pigment blue 15: 35 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

Obtain toner (t-3) in the mode identical with toner production example 7.Table 8 illustrates the composition of the toner (t-3) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(toner production example 10)

Produce toner (t-4) by using following material and following production method.

Low softening point resin (L-6) 90 mass parts

High softening point resin (H-4) 10 mass parts

C.I. pigment blue 15: 35 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

Obtain toner (t-4) in the mode identical with toner production example 7.Table 8 illustrates the composition of the toner (t-4) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(toner production example 11)

Produce toner (t-5) by using following material and following production method.

Low softening point resin (L-3) 30 mass parts

High softening point resin (H-5) 70 mass parts

C.I. pigment blue 15: 35 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.5 mass parts

Obtain toner (t-5) in the mode identical with toner production example 7.Table 8 illustrates the composition of the toner (t-5) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(toner production example 12)

Produce toner (t-6) by using following material and following production method.

Middle softening point resin (M-2) 100 mass parts

Masterbatch (P-1) 10 mass parts

N PARAFFIN ﹠ HEAVY NORMAL PARAFFIN (W-1: 7 mass parts 75 ℃ of fusing points)

3,5-di-tert-butyl salicylic acid aluminium compound (C-1) 0.7 mass parts

Obtain toner (t-6) in the mode identical with toner production example 1.Table 8 illustrates the composition of the toner (t-6) that obtains herein, and table 9 illustrates the physical property of toner, and Figure 16 illustrates the chart 2 of toner.

(the coating carrier is produced example)

By the nuclear that uses following manufacture of materials magnetic fine grained to disperse.

Phenol 10 mass parts

Formalin (37-quality % aqueous solution) 6 mass parts

Magnetic-particle (number average bead diameter D1=0.28 μ m, magnetization 75Am ²/ kg is than resistance 5.5 * 10 ⁵Ω cm) 84 mass parts

The ammoniacal liquor of above-mentioned material and 5 mass parts, 28 quality % and 10 mass parts water are packed in the flask, and whole materials were heated to 85 ℃ and remain on and stir simultaneously under this temperature and mix in 30 minutes.Gains are carried out polyreaction 3 hours to solidify.Afterwards, cured product is cooled to 30 ℃, and further water is added in the product.Afterwards, remove supernatant.Precipitation is washed with water, then air drying.Next, gains are dry down in decompression (below the 5hPa) under 60 ℃ temperature, obtain wherein to divide the sperromagnetism nuclear that fine grain magnetic fine grained disperses thus.

Subsequently, the methyl methacrylate macromonomer, 50 mass parts methyl methacrylates and the 50 mass parts cyclohexyl methacrylates that 5 mass parts are expressed from the next and have olefinic (ethylenically) unsaturated group and 5,000 weight-average molecular weight in an one end are added in the four neck flasks that are provided with reflux condenser, thermometer, nitrogen suction lead and abrasive type mixing plant.In addition, the two isobutyl cyanides of 100 mass parts toluene, 100 mass parts MEKs and 2.5 mass parts azos are joined flask, and in nitrogen stream, whole materials were kept 10 hours down at 80 ℃, obtain to be used for the resin solution (solid content 35 quality %) of coating material thus.

Has the beaded glass of 0.5mm pearl diameter separately in sand mill (RMH-03 type by using, by AIMEXCO., Ltd. make) in 2 mass parts silicone particles (number average bead diameter 0.2 μ m), 1 mass parts carbon black (number average bead diameter 35nm, DBP oil absorption 50ml/100g) and 70 mass parts toluene be scattered in the resin solution that is used for coating material of 30 mass parts gained, thereby obtain coating material.

Subsequently, 6 mass parts coating materials are injected into jet blower on the nuclear of 100 mass parts magnetic fine graineds dispersion, simultaneously by using fluidized bed coating apparatus (SPIR-A-FLOW is made by FREUND) will examine 80 ℃ of following fluidisations.Afterwards, with solvent evaporation and dry, simultaneously with the gains fluidisation, the surface that will examine is coated with coating material thus under 100 ℃.The nuclear that the magnetic fine grained of coating is disperseed is with the sieve classification with 75 μ m apertures, obtains to have number average bead diameter 35 μ m thus, than resistance 3.0 * 10 ⁸Ω cm, true specific gravity 3.6g/cm ³, the magnetization (σ 1000) 55.5Am ²/ kg and remanent magnetization 5.5Am ²The coating carrier of/kg.

(embodiment 1)

At first, produce developer.8 mass parts toners (T-1) are added in the above-mentioned coating carrier of 92 mass parts, and whole materials are mixed with V-Mixer, obtain developer thus.

Next, with as shown in Figure 2 this band developing cell be used to estimate the photographic fixing ability.Fixing conditions is as follows: fixation rate is 300mm/sec, and the fusing nip width is that 30mm and fusing nip pressure are 0.15MPa.

The reforming equipment of the panchromatic duplicating machine IRC3220N that will be made by Canon Inc. is used to estimate development capability and transfer printing ability.The duplicating machine transformation also can be exported 70 by per minute with the processing speed with 300mm/s.The reforming equipment that it should be noted that IRC3220N also is used for output image to be used for the photographic fixing ability assessment.

(23 ℃ of ambient temperature and moisture environment, 50%RH), the low wet environment of normal temperature is (23 ℃, 5%RH), the low temperature and low humidity environment (15 ℃, 10%RH) and hot and humid environment (30 ℃, one of 80%RH) down with image output and estimate separately photographic fixing ability, development capability and transfer printing ability.It should be noted that following assessment item and the evaluation criterion of illustrating.Table 10,12 and 14 illustrates the evaluation result that is obtained.

It should be noted that hereinafter above-mentioned ambient temperature and moisture environment, the low wet environment of above-mentioned normal temperature, above-mentioned low temperature and low humidity environment and above-mentioned hot and humid environment can be called N/N environment, N/L environment, L/L environment and H/H environment.

(estimating the project of photographic fixing ability)

(estimating low temperature fixation performance, glossiness and colourity)

20%) and have a 105g/m at first, uses as shown in Figure 3 this A4 image (printing rate: ²The paper of basic weight is as recording materials.Output image regulates the development bias voltage simultaneously so that the toner fixed amount on recording materials is 1.2mg/cm ²The gained image is carried out damping 24 hours under the L/L environment.

Subsequently, under the L/L environment, estimate the low-temperature fixing of toner.When the temperature of photographic fixing band is raise in 100 to 200 ℃ scope with 5 ℃ increment, by carrying out the image of damping.

The toner image part of the image that will pass through is by having

(copper: 798g) the cylindric roller of size is reciprocal 5 times, thereby folding with the shape of intersecting for 60mm * 40mm.After opening, quadrangular prism shape (square polar) (copper: lens cleaning paper (the DusperK3-half cut of section 198g) around the thick metering of the wide 47mm of the long 22mm of 22mm, make by OZU CORPORATION) with image friction ten times, the temperature of toner image being peeled off place below 25% is defined as fixing temperature.The percent of peeling off with Flame Image Process system (Personal IAS) measurement image.In addition, in estimating the toner glossiness, by using the gloss value of the image measurement toner that when the temperature of photographic fixing band is 160 ℃, passes through.Under 60 ° measured angular, measure gloss value with glossmeter (PG-1 is made by NIPPONDENSHOKU).

In estimating toner colourity, measure the colourity of the image that is used to measure gloss value.Under 2 ° observation visual angle, also use D50 as observing light source measurement colourity with chromoscope (Spectrolino is made by GRETAGMACBETH).

(estimating hot stained property)

At first, use this A4 image as shown in Figure 4 and have 64g/m ²The paper of basic weight is as recording materials.Output image regulates the development bias voltage simultaneously so that the toner fixed amount on the recording materials is 0.2mg/cm ²The gained image is carried out damping 24 hours under the N/L environment.

Subsequently, toner is estimated hot stained property under the N/L environment.When the temperature of photographic fixing band is raise in 120 to 220 ℃ scope with 5 ℃ increment, the image that carries out damping is passed through.Measure the concentration that hazes in the zone except that the toner image part of the image that passes through.With reflection of the concentration (TC-6DS, make by Tokyo Denshoku) measure the concentration that hazes, the minimum value of the reflection of the concentration of image is deducted the value that obtains from the maximal value of reflection of the concentration become the unchallenged temperature of hot stained property that the temperature below 0.5 is judged to be.

(evaluation separation property)

15%) and have a 64g/m at first, uses as shown in Figure 5 this A5 image (printing rate: ²The paper of basic weight is as recording materials.Output image regulates the development bias voltage simultaneously so that the toner fixed amount on the recording materials is 1.2mg/cm ²The gained image is carried out damping 24 hours under the H/H environment.

Subsequently, toner is estimated separation property under the H/H environment.When the temperature of photographic fixing band is raise in 100 to 220 ℃ scope with 5 ℃ increment, the image that carries out damping is passed through.Will by the time release graphics picture and the temperature of not twining around the photographic fixing band is judged to be the temperature of separation of images.In addition, carry out the separation property evaluation based on following standard.

A: the temperature province of separation of images is arranged at more than 70 ℃.

B: the temperature province of separation of images is arranged at more than 50 ℃ to being lower than 70 ℃.

C: the temperature province of separation of images is arranged at more than 30 ℃ to being lower than 50 ℃.

D: the temperature province of separation of images is arranged at more than 10 ℃ to being lower than 30 ℃.

E: the temperature province of separation of images is arranged at is lower than 10 ℃.

(estimating the project of development capability and transfer printing ability)

(evaluation image color)

10%) and have a 80g/m at first, uses as shown in Figure 6 this A4 image (printing rate: ²The paper of basic weight is as recording materials.When regulating the development bias voltage so that the toner fixed amount on the recording materials is 0.6mg/cm ²The time, output reaches 10,000 images under each N/N, N/L and H/H environment.Measure the concentration of each gained image with densimeter X-Rite500 type, and the mean value of six measured values is defined as image color at six some places.

(shadow tone (HT) homogeneity)

Regulate the development bias voltage so that the toner fixed amount on the recording materials is 0.3mg/cm at image output initial period with after exporting 10,000 simultaneously at output image under the H/H environment ²Measure the reflection density of each gained image with densimeter X-Rite500 type at six some places, and based on following standard evaluation image.

The maximal value of six points of A:()-(minimum value of six points) for being lower than 0.05.

The maximal value of six points of B:()-(minimum value of six points) be to being lower than 0.10 more than 0.05.

The maximal value of six points of C:()-(minimum value of six points) be to being lower than 0.15 more than 0.10.

The maximal value of six points of D:()-(minimum value of six points) be to being lower than 0.20 more than 0.15.

The maximal value of six points of E:()-(minimum value of six points) be more than 0.20.

(evaluation transfer efficiency)

In this A4 image (the printing rate: 10%) regulate the development bias voltage so that the toner fixed amount on the recording materials is 0.6mg/cm at image output initial period with after exporting 10,000 simultaneously as shown in Figure 6 of output under each N/N, N/L and the H/H environment ²Image when output, the transfer printing residual toner on the Electrifier frame, photoreceptor of taking a sample immediately after the toner of transfer printing on the transfer materials and the transfer printing of taking a sample immediately after the transfer printing.Sampling method comprises: (by the Super Stick KA PET25 (A) of Lintec Corporation manufacturing) peels off all toner images with band; This band is adhered on the blank sheet of paper; And from the reflection density of above-mentioned band with densimeter X-Rite500 type measurement band.Calculate transfer efficiency from following formula.

Transfer efficiency=(peeling off the mean concentration-with independent concentration of six points of the band of transfer printing toner)/((peeling off the mean concentration-with independent concentration of six points of the band of transfer printing toner)+(peeling off the mean concentration-with independent concentration of six points of the band of transfer printing residual toner)).

(estimating blank)

Initial period output this two A4 image as shown in Figure 7 of under the H/H environment, exporting at image.Similarly, exporting output this two A4 image as shown in Figure 7 after 10,000 under this environment.For blank, based on each gained image of following standard evaluation.

A: line image shows does not have blank, so image has high line repeatability.

B: observe slight blank with small-sized magnifier, but in visual observation, do not cause problem.

C: in the thinnest line, observe visually blank (line width: 0.1mm).

D: in the second the thinnest line, observe visually blank (line width: 0.2mm).

E: in the thickest line, observe visually blank (line width: 0.3mm).

(embodiment 2 to 6)

In the toner (T-2) to (T-6) that use is shown in Table 8 any replaces the toner (T-1) among the embodiment, with embodiment 1 in identical mode carry out the evaluation of projects.Table 10,12 and 14 illustrates the result of evaluation.

(comparative example 1 to 6)

In the toner (t-1) to (t-6) that use is shown in Table 8 any replaces the toner (T-1) among the embodiment 1, with embodiment 1 in identical mode carry out the evaluation of projects.Table 11,13 and 15 illustrates the result of evaluation.

Table 10

Table 10. embodiment (estimating the photographic fixing ability)

Table 11

Table 11. comparative example (estimating the photographic fixing ability)

Table 12

Table 12. embodiment (evaluation image color)

Table 13

Table 13. comparative example (evaluation image color)

Table 14

Table 14. embodiment (estimating the transfer printing ability)

Table 15

Table 15. comparative example (estimating the transfer printing ability)

Claims (4)

1. toner, it comprises the toner-particle that comprises resin glue and colorant separately at least,

Wherein said resin glue has low softening point resin and high softening point resin,

Described low softening point resin has more than 80.0 ℃ to being lower than 110.0 ℃ softening point and having polyester unit and the vinyl-based copolymer unit,

Described high softening point resin has more than 110.0 ℃ to the softening point below 145.0 ℃ and has polyester unit and the vinyl-based copolymer unit,

Ratio between the quality of described low softening point resin and the quality of described high softening point resin in 50/50 to 90/10 scope and

Wherein, when making described toner carry out soxhlet extraction in the time of 2 hours with THF, the tetrahydrofuran of the resin glue in the toner (THF) insoluble substance is represented by A (quality %), when making described toner carry out soxhlet extraction in the time of 4 hours with THF, the THF insoluble substance of the resin glue in the toner is represented by B (quality %), when making described toner carry out soxhlet extraction in the time of 8 hours with THF, the THF insoluble substance of the resin glue in the toner is represented by C (quality %), and when making described toner carry out soxhlet extraction in the time of 16 hours with THF, under the situation of the THF insoluble substance of the resin glue in the toner by D (quality %) expression, A, B, C and D satisfy following expression formula (1):

(A-B)/2＞(B-C)/4＞(C-D)/8 …(1)

Wherein 40＜A≤75 (quality %) and 1.0＜D＜40 (quality %).

2. toner according to claim 1 locates to have the highest endothermic peak at 50 to 110 ℃ in the endothermic curve of wherein said toner in differential scanning calorimetry (D SC).

3. storage elastic modulus G ' (140 ℃) that toner according to claim 1, wherein said toner have under 140 ℃ are 1.0 * 10 ³DN/m ²Below to being lower than 1.0 * 10 ⁵DN/m ²

4. toner according to claim 1, wherein said toner has more than 0.945 to the average circularity below 0.990, described average circularity is by following acquisition: more than 0.200 to the circularity scope below 1.000, to be that the circularity that the streaming particle image measurement mechanism of 512 * 512 pixels is measured is divided into 800 parts and analyzes described circularity with having Flame Image Process resolution, wherein every pixel be 0.37 μ m * 0.37 μ m.

Images